Photosensitive composition

ABSTRACT

A photosensitive composition for pulse exposure includes: a near infrared absorber A; a photoinitiator B; and a compound C that is cured by reacting with an active species generated from the photoinitiator B.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of PCT International Application No.PCT/JP2019/007063 filed on Feb. 25, 2019, which claims priority under 35U.S.C § 119(a) to Japanese Patent Application No. 2018-035140 filed onFeb. 28, 2018. Each of the above application(s) is hereby expresslyincorporated by reference, in its entirety, into the presentapplication.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention relates to a photosensitive composition includinga near infrared absorber. More specifically, a photosensitivecomposition used for a near infrared cut filter, a near infraredtransmitting filter, or the like.

2. Description of the Related Art

A digital camera, a mobile phone equipped with a camera, or the like hasbeen widely used, and a demand for a solid-state imaging element such asa charge coupled device (CCD) image sensor has increased significantly.As a key device of a display or an optical element, a color filter isused. Typically, the color filter includes pixels (colored patterns) ofthree primary colors including red, green, and blue and has a functionof separating transmitted light into three primary colors.

The color filter can be formed using a photosensitive compositionincluding a colorant. In addition, JP2012-532334A describes aphotosensitive color resin composition for manufacturing a color filterfor a solid-state imaging element using an ultra-short wavelengthexposing device of 300 nm or less.

In addition, in a light receiving section of this solid-state imagingelement, a silicon photodiode having sensitivity to infrared light isused. Therefore, visibility may be corrected using a near infrared cutfilter. The near infrared cut filter is manufactured, for example, usinga photosensitive composition including a near infrared absorber.

SUMMARY OF THE INVENTION

In the related art, a near infrared cut filter has been used as a flatfilm. Recently, it has also been considered to form a pattern on a nearinfrared cut filter. For example, the use of a laminate in which eachpixel (for example, a red pixel, a blue pixel, or a green pixel) of acolor filter is formed on a pattern of a near infrared cut filter hasbeen considered.

On the other hand, a near infrared absorber has high transmittance withrespect to light such as an i-ray used for exposure. Therefore, in acase where a photosensitive composition including a near infraredabsorber is exposed through a mask, a non-exposed portion at a mask edgemay be exposed to reflected light or scattered light from a support orthe like. In order to form a film that is sufficiently cured, a certainlevel of exposure dose is required. However, in a case where theexposure dose is excessively high, the reaction also progresses in aportion covered with a mask such that solubility in a developerdeteriorates. As a result, the line width of the obtained pattern may bethicker than a desired value or a residue is likely to be formed betweenthe patterns. Therefore, further improvement of performance for patternformability regarding a photosensitive composition including a nearinfrared absorber is desired.

JP2012-532334A does not describe a composition including a near infraredabsorber regarding a color filter.

Accordingly, an object of the present invention is to provide aphotosensitive composition having excellent pattern formability.

As a result of a thorough investigation, the present inventors foundthat excellent pattern formability can be obtained by exposing aphotosensitive composition including a near infrared absorber to pulsesof light to form a pattern, thereby completing the present invention.Accordingly, the present invention provides the following.

<1> A photosensitive composition for pulse exposure comprising:

a near infrared absorber A;

a photoinitiator B; and

a compound C that is cured by reacting with an active species generatedfrom the photoinitiator B.

<2> The photosensitive composition according to <1>,

in which an A/B that is a ratio of an absorbance A of the photosensitivecomposition with respect to light having a wavelength of 248 nm to anabsorbance B of the photosensitive composition with respect to lighthaving a wavelength of 365 nm is 3.4 or higher.

<3> The photosensitive composition according to <1> or <2>,

in which the photoinitiator B includes an photoinitiator b1 thatsatisfies the following condition 1,

condition 1: after a propylene glycol monomethyl ether acetate solutionincluding 0.035 mmol/L of the photoinitiator b1 is exposed to pulses oflight having a wavelength of 355 nm under conditions of a maximuminstantaneous illuminance of 375000000 W/m², pulse duration: 8nanoseconds, and frequency: 10 Hz, a quantum yield q₃₅₅ is 0.05 orhigher.

<4> The photosensitive composition according to <3>,

in which the quantum yield q₃₅₅ of the photoinitiator b1 is 0.10 orhigher.

<5> The photosensitive composition according to <3> or <4>,

in which the photoinitiator b1 satisfies the following condition 2,

condition 2: after a film having a thickness of 1.0 μm and including 5mass % of the photoinitiator b1 and 95 mass % of a resin is exposed topulses of light having a wavelength of 265 nm under conditions of amaximum instantaneous illuminance of 375000000 W/m², pulse duration: 8nanoseconds, and frequency: 10 Hz, a quantum yield q₂₆₅ is 0.05 orhigher.

<6> The photosensitive composition according to <5>,

in which the quantum yield q₂₆₅ of the photoinitiator b1 is 0.10 orhigher.

<7> The photosensitive composition according to any one of <3> to <6>,

in which the photoinitiator b1 satisfies the following condition 3,

condition 3: after a film including 5 mass % of the photoinitiator b1and a resin is exposed to one pulse of light having a wavelength in awavelength range of 248 to 365 nm under conditions of a maximuminstantaneous illuminance of 62/500,0000 W/m², pulse duration: 8nanoseconds, and frequency: 10 Hz, an active species concentration inthe film reaches 0.000000001 mmol or higher per 1 cm² of the film.

<8> The photosensitive composition according to <7>,

in which the active species concentration in the film the photoinitiatorb1 reaches 0.0000001 mmol or higher per 1 cm² of the film under thecondition 3.

<9> The photosensitive composition according to any one of <1> to <8>,

in which a content of the near infrared absorber A is 15 mass % orhigher with respect to a total solid content of the photosensitivecomposition.

<10> The photosensitive composition according to any one of <1> to <9>,

in which a content of the compound C is 5% to 30 mass % with respect toa total solid content of the photosensitive composition.

<11> The photosensitive composition according to any one of <1> to <10>,

in which the photoinitiator B is a photoradical polymerizationinitiator, and

the compound C is a radically polymerizable compound.

<12> The photosensitive composition according to <11>,

in which the radically polymerizable compound includes a radicallypolymerizable monomer.

<13> The photosensitive composition according to <12>,

in which a polymerizable group value of the radically polymerizablemonomer is 10.5 mmol/g or higher.

<14> The photosensitive composition according to any one of <11> to<13>,

in which the photoradical polymerization initiator is at least onecompound selected from an alkylphenone compound, an acylphosphinecompound, a benzophenone compound, a thioxanthone compound, a triazinecompound, or an oxime compound.

<15> The photosensitive composition according to any one of <1> to <14>,further comprising:

an ultraviolet absorber.

<16> The photosensitive composition according to <15>,

in which a content of the ultraviolet absorber is 0.01% to 7 mass % withrespect to a total solid content of the photosensitive composition.

<17> The photosensitive composition according to any one of <1> to <16>,further comprising:

an antioxidant.

<18> The photosensitive composition according to <17>,

in which a content of the antioxidant is 0.1% to 5 mass % with respectto a total solid content of the photosensitive composition.

<19> The photosensitive composition according to any one of <1> to <18>,which is a composition for a near infrared cut filter.

<20> The photosensitive composition according to any one of <1> to <18>,which is a photosensitive composition for a near infrared transmittingfilter.

<21> The photosensitive composition according to any one of <1> to <20>,which is a photosensitive composition for pulse exposure to light havinga wavelength of 300 nm or shorter.

<22> The photosensitive composition according to any one of <1> to <21>,which is a photosensitive composition for pulse exposure under acondition of a maximum instantaneous illuminance of 50000000 W/m² orhigher.

According to the present invention, a photosensitive composition havingexcellent pattern formability can be provided.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Hereinafter, the details of the present invention will be described.

In this specification, numerical ranges represented by “to” includenumerical values before and after “to” as lower limit values and upperlimit values.

In this specification, unless specified as a substituted group or as anunsubstituted group, a group (atomic group) denotes not only a group(atomic group) having no substituent but also a group (atomic group)having a substituent. For example, “alkyl group” denotes not only analkyl group having no substituent (unsubstituted alkyl group) but alsoan alkyl group having a substituent (substituted alkyl group).

In this specification, “(meth)allyl group” denotes either or both ofallyl and methallyl, “(meth)acrylate” denotes either or both of acrylateor methacrylate, “(meth)acryl” denotes either or both of acryl andmethacryl, and “(meth)acryloyl” denotes either or both of acryloyl andmethacryloyl.

In this specification, a weight-average molecular weight and anumber-average molecular weight denote values in terms of polystyrenemeasured by gel permeation chromatography (GPC).

In this specification, near infrared light denotes light in a wavelengthrange of 700 to 2500 nm.

In this specification, a total solid content denotes the total mass ofall the components of the composition excluding a solvent.

In this specification, the term “step” denotes not only an individualstep but also a step which is not clearly distinguishable from anotherstep as long as an effect expected from the step can be achieved.

<Photosensitive Composition>

A photosensitive composition for pulse exposure according to anembodiment of the present invention comprises: a near infrared absorberA; a photoinitiator B; and a compound C that is cured by reacting withan active species generated from the photoinitiator B.

The photosensitive composition according to the embodiment of thepresent invention has excellent pattern formability. A fine pattern canbe formed by exposing the photosensitive composition according to theembodiment of the present invention to pulses of light. The reason whythis effect is obtained is presumed to be as follows. That is, byexposing the photosensitive composition including the near infraredabsorber A, the photoinitiator B, and the compound C to pulses of light,a large amount of an active species such as a radical is instantaneouslygenerated from the photoinitiator B in the exposed portion. As a result,the compound C can be efficiently cured due to an effect of, forexample, suppressing deactivation caused by oxygen. As a result, it ispresumed that only the exposed portion of the photosensitive compositioncan be selectively cured by the pulse exposure such that a pattern canbe formed along a mask shape. Therefore, it is presumed that thephotosensitive composition according to the embodiment of the presentinvention has excellent pattern formability. The pulse exposuredescribed in the present invention refers to an exposure method in whichlight irradiation and pause are repeated in a cycle of a short period oftime (for example, a level of milliseconds).

The photosensitive composition according to the embodiment of thepresent invention is a photosensitive composition for pulse exposure.The light used for the exposure may be light having a wavelength oflonger than 300 nm or light having a wavelength of 300 nm or shorter.From the viewpoint of easily obtaining higher pattern formability,curing properties, and the like, the light used for the exposure ispreferably light having a wavelength of 300 nm or shorter, morepreferably light having a wavelength of 270 nm or shorter, and stillmore preferably light having a wavelength of 250 nm or shorter. Inaddition, the above-described light is preferably light having awavelength of 180 nm or longer. Specific examples of the light include aKrF ray (wavelength: 248 nm) and an ArF ray (wavelength: 193 nm). Fromthe viewpoint of easily obtaining higher pattern formability, curingproperties, and the like, a KrF ray (wavelength: 248 nm) is preferable.

It is preferable that the exposure condition of the pulse exposure isthe following condition. From the viewpoint of instantaneouslygenerating a large amount of an active species such as a radical easily,the pulse duration is preferably 100 nanoseconds (ns) or shorter, morepreferably 50 nanoseconds or shorter, and still more preferably 30nanoseconds or shorter. The lower limit of the pulse duration is notparticularly limited and may be 1 femtoseconds (fs) or longer or 10femtoseconds (fs) or longer. From the viewpoint of easily thermallypolymerizing the compound C due to exposure heat, the frequency ispreferably 1 kHz or higher, more preferably 2 kHz or higher, and stillmore preferably 4 kHz or higher. From the viewpoint of easilysuppressing deformation of a substrate or the like caused by exposureheat, the upper limit of the frequency is preferably 50 kHz or lower,more preferably 20 kHz or lower, and still more preferably 10 kHz orlower. From the viewpoint of curing properties, the maximuminstantaneous illuminance is preferably 50000000 W/m² or higher, morepreferably 100000000 W/m² or higher, and still more preferably 200000000W/m² or higher. In addition, from the viewpoint of high illuminancereciprocity failure, the upper limit of the maximum instantaneousilluminance is preferably 1000000000 W/m² or lower, more preferably800000000 W/m² or lower, and still more preferably 500000000 W/m² orlower. The pulse duration refers to the length of time during whichlight is irradiated during a pulse period. In addition, the frequencyrefers to the number of pulse periods per second. In addition, themaximum instantaneous illuminance refers to an average illuminancewithin a time during which light is irradiated in a pulse period. Inaddition, the pulse period refers to a period in which light irradiationand pause during pulse exposure are set as one cycle.

It is preferable that the photosensitive composition according to theembodiment of the present invention satisfies spectral characteristicsin which an A/B that is a ratio of an absorbance A with respect to lighthaving a wavelength of 248 nm to an absorbance B with respect to lighthaving a wavelength of 365 nm is 3.4 or higher. By the photosensitivecomposition according to the embodiment of the present inventionsatisfying the spectral characteristics, even in a case where thecontent of the photopolymerization initiator is low, excellentsensitivity properties can be obtained, and an ultrafine pattern with ahigh resolution can be formed even at a low exposure dose. A/B ispreferably 3.4 or higher, more preferably 3.45 or higher, and still morepreferably 3.5 or higher. From the viewpoint of easily suppressing areverse tapered shape due to insufficient curing of a pattern lowerportion, the upper limit is preferably 4.0 or lower.

The photosensitive composition according to the embodiment of thepresent invention can be preferably used as a photosensitive compositionfor a near infrared cut filter or a photosensitive composition for anear infrared transmitting filter. In addition, the photosensitivecomposition according to the embodiment of the present invention can bepreferably used as a photosensitive composition for a solid-stateimaging element. In the present invention, “near infrared cut filter”refers to a filter that allows transmission of light (visible light) inthe visible range and blocks at least a part of light (near infraredlight) in the near infrared range. The near infrared cut filter may be afilter that allows transmission of light in the entire wavelength rangeof the visible range, or may be a filter that allows transmission oflight in a specific wavelength range of the visible range and blockslight in another specific wavelength range of the visible range. Inaddition, in the present invention, “near infrared transmitting filter”refers to a filter that blocks visible light and allows transmission ofat least a part of near infrared light.

In a case where the photosensitive composition according to theembodiment of the present invention is used as a photosensitivecomposition for a near infrared cut filter, it is preferable that thephotosensitive composition according to the embodiment of the presentinvention has a maximum absorption wavelength in a wavelength range of700 to 1800 nm, it is more preferable that the photosensitivecomposition according to the embodiment of the present invention has amaximum absorption wavelength in a wavelength range of 700 to 1300 nm,and it is still more preferable that the photosensitive compositionaccording to the embodiment of the present invention has a maximumabsorption wavelength in a wavelength range of 700 to 1000 nm. Inaddition, it is preferable that the photosensitive composition accordingto the embodiment of the present invention satisfies spectralcharacteristics in which A₁/A₂ that is a ratio of a maximum value A₁ ofan absorbance in a wavelength range of 400 to 600 nm to an absorbance A₂at the maximum absorption wavelength is 0.30 or lower. With thephotosensitive composition having the spectral characteristics, a nearinfrared cut filter having excellent near infrared blocking propertiesand excellent visible transparency can be formed. A₁/A₂ is preferably0.20 or lower, more preferably 0.15 or lower, and still more preferably0.10 or lower.

In a case where the photosensitive composition according to theembodiment of the present invention is used as a photosensitivecomposition for a near infrared transmitting filter, it is preferablethat the photosensitive composition according to the embodiment of thepresent invention satisfies spectral characteristics in which a ratioAmin/Bmax of a minimum value Amin of an absorbance of the photosensitivecomposition in a wavelength range of 400 to 640 nm to a maximum valueBmax of an absorbance of the photosensitive composition in a wavelengthrange of 1100 to 1300 nm is 5 or higher. Amin/Bmax is more preferably7.5 or higher, still more preferably 15 or higher, and still morepreferably 30 or higher.

An absorbance Aλ at a wavelength λ is defined by the followingExpression (1).

Aλ=−log(Tλ/100)  (1)

Aλ represents the absorbance at the wavelength λ, and Tλ represents atransmittance (%) at the wavelength λ.

In the present invention, a value of the absorbance may be a valuemeasured in the form of a solution or a value of a film which is formedusing the photosensitive composition. In a case where the absorbance ismeasured in the form of the film, it is preferable that the absorbanceis measured using a film that is formed by applying the photosensitivecomposition to a glass substrate using a method such as spin coatingsuch that the thickness of the dried film is a predetermined value, anddrying the applied composition using a hot plate at 100° C. for 120seconds.

In a case where the photosensitive composition according to theembodiment of the present invention is used as a photosensitivecomposition for a near infrared transmitting filter, it is morepreferable that the photosensitive composition according to theembodiment of the present invention satisfies any one of the followingspectral characteristics (11) to (14).

(11): A ratio Amin1/Bmax1 of a minimum value Amin1 of an absorbance ofthe photosensitive composition in a wavelength range of 400 to 640 nm toa maximum value Bmax1 of an absorbance of the photosensitive compositionin a wavelength range of 800 to 1300 nm is 5 or higher, preferably 7.5or higher, more preferably 15 or higher, and still more preferably 30 orhigher. In this aspect, a film that can block light in a wavelengthrange of 400 to 640 nm and allows transmission of light having awavelength of 720 nm or longer can be formed.

(12): A ratio Amin2/Bmax2 of a minimum value Amin2 of an absorbance ofthe photosensitive composition in a wavelength range of 400 to 750 nm toa maximum value Bmax2 of an absorbance of the photosensitive compositionin a wavelength range of 900 to 1300 nm is 5 or higher, preferably 7.5or higher, more preferably 15 or higher, and still more preferably 30 orhigher. In this aspect, a film that can block light in a wavelengthrange of 400 to 750 nm and allows transmission of light having awavelength of 850 nm or longer can be formed.

(13): A ratio Amin3/Bmax3 of a minimum value Amin3 of an absorbance ofthe photosensitive composition in a wavelength range of 400 to 850 nm toa maximum value Bmax3 of an absorbance of the photosensitive compositionin a wavelength range of 1000 to 1300 nm is 5 or higher, preferably 7.5or higher, more preferably 15 or higher, and still more preferably 30 orhigher. In this aspect, a film that can block light in a wavelengthrange of 400 to 850 nm and allows transmission of light having awavelength of 940 nm or longer can be formed.

(14): A ratio Amin4/Bmax4 of a minimum value Amin4 of an absorbance ofthe photosensitive composition in a wavelength range of 400 to 950 nm toa maximum value Bmax4 of an absorbance of the photosensitive compositionin a wavelength range of 1100 to 1300 nm is 5 or higher, preferably 7.5or higher, more preferably 15 or higher, and still more preferably 30 orhigher. In this aspect, a film that can block light in a wavelengthrange of 400 to 950 nm and allows transmission of light having awavelength of 1040 nm or longer can be formed.

Hereinafter, each of the components used in the photosensitivecomposition according to the embodiment of the present invention will bedescribed.

<<Near Infrared Absorber A>>

The photosensitive composition according to the embodiment of thepresent invention includes a near infrared absorber A (hereinafter,simply referred to as “near infrared absorber”). The near infraredabsorber may be an organic compound or an inorganic compound. Inaddition, the near infrared absorber may be a pigment (also referred toas “near infrared absorbing pigment”) or a dye (also referred to as“near infrared absorbing dye”). In addition, it is preferable that thenear infrared absorbing dye and the near infrared absorbing pigment areused in combination. In a case where the near infrared absorbing dye andthe near infrared absorbing pigment are used in combination, a massratio near infrared absorbing dye:near infrared absorbing pigment of thenear infrared absorbing dye to the near infrared absorbing pigment ispreferably 99.9:0.1 to 0.1:99.9, more preferably 99.9:0.1 to 10:90, andstill more preferably 99.9:0.1 to 20:80. The solubility of the nearinfrared absorbing dye in 100 g of at least one solvent selected fromcyclopentanone, cyclohexanone, or dipropylene glycol monomethyl ether at23° C. is preferably 1 g or higher, more preferably 2 g or higher, andstill more preferably 5 g or higher. In addition, a solubility of thenear infrared absorbing pigment in 100 g of each solvent ofcyclopentanone, cyclohexanone, or dipropylene glycol monomethyl ether at23° C. is preferably lower than 1 g, more preferably 0.1 g or lower, andstill more preferably 0.01 g or lower.

The near infrared absorber is preferably a compound having a maximumabsorption wavelength in a wavelength range of 700 to 1800 nm, morepreferably a compound having a maximum absorption wavelength in awavelength range of 700 to 1300 nm, and still more preferably a compoundhaving a maximum absorption wavelength in a wavelength range of 700 to1000 nm. In addition, in the near infrared absorber, a ratio A¹/A² of anabsorbance A¹ at a wavelength of 500 nm to an absorbance A² at themaximum absorption wavelength is preferably 0.08 or lower and morepreferably 0.04 or lower. In this aspect, a film having excellentvisible transparency and near infrared blocking properties can be easilymanufactured.

In the present invention, as the near infrared absorber, at least twocompounds having different maximum absorption wavelengths are preferablyused. In this aspect, the waveform of the absorption spectrum of theobtained film is wider than that in a case where one near infraredabsorber is used, and the film can block near infrared light in a widewavelength range.

Examples of the inorganic compound used as the near infrared absorberinclude a metal oxide and a metal boride. Examples of the metal oxideinclude indium tin oxide, antimony tin oxide, zinc oxide, Al-doped zincoxide, fluorine-doped tin dioxide, niobium-doped titanium dioxide, andtungsten oxide. The details of the tungsten oxide can be found inparagraph “0080” of JP2016-006476A, the content of which is incorporatedherein by reference. Examples of the metal boride include lanthanumboride. Examples of a commercially available product of the lanthanumboride include LaB₆—F (manufactured by Japan New Metals Co., Ltd.).

It is preferable that the organic compound used as the near infraredabsorber is a compound that includes a π-conjugated plane having amonocyclic or fused aromatic ring. The number of atoms forming theπ-conjugated plane other than hydrogen is preferably 6 or more, morepreferably 14 or more, still more preferably 20 or more, still morepreferably 25 or more, and still more preferably 30 or more. Forexample, the upper limit is preferably 80 or less and more preferably 50or less.

In addition, the number of monocyclic or fused aromatic rings includedin the π-conjugated plane is preferably 2 or more, more preferably 3 ormore, and still more preferably 4 or more. The upper limit is preferably100 or less, more preferably 50 or less, and still more preferably 30 orless. Examples of the aromatic ring include a benzene ring, anaphthalene ring, an indene ring, an azulene ring, a heptalene ring, anindacene ring, a perylene ring, a pentacene ring, a quaterrylene ring,an acenaphthene ring, a phenanthrene ring, an anthracene ring, anaphthacene ring, a chrysene ring, a triphenylene ring, a fluorene ring,a pyridine ring, a quinoline ring, an isoquinoline ring, an imidazolering, a benzimidazole ring, a pyrazole ring, a thiazole ring, abenzothiazole ring, a triazole ring, a benzotriazole ring, an oxazolering, a benzoxazole ring, an imidazoline ring, a pyrazine ring, aquinoxaline ring, a pyrimidine ring, a quinazoline ring, a pyridazinering, a triazine ring, a pyrrole ring, an indole ring, an isoindolering, a carbazole ring, a pyran ring, a thiopyran ring, and a fused ringincluding the above-described ring.

As the organic compound used as the near infrared absorber, at least oneselected from a pyrrolopyrrole compound, a cyanine compound, asquarylium compound, a phthalocyanine compound, a naphthalocyaninecompound, a rylene compound, a merocyanine compound, a croconiumcompound, an oxonol compound, an iminium compound, a dithiol compound, atriarylmethane compound, a pyrromethene compound, an azomethinecompound, an anthraquinone compound, or a dibenzofuranone compound ispreferable, at least one selected from a pyrrolopyrrole compound, acyanine compound, a squarylium compound, a croconium compound, a rylenecompound, or an iminium compound is more preferable, at least oneselected from a pyrrolopyrrole compound, a cyanine compound, asquarylium compound, or a croconium compound is still more preferable,and a pyrrolopyrrole compound is still more preferable. Examples of thephthalocyanine compound include a compound described in paragraph “0093”of JP2012-077153A, oxytitaniumphthalocyanine described inJP2006-343631A, a compound described in paragraphs “0013” to “0029” ofJP2013-195480A, vanadium phthalocyanine described in JP6081771B, thecontents of which are incorporated herein by reference. Examples of thenaphthalocyanine compound include a compound described in paragraph“0093” of JP2012-077153A, the content of which is incorporated herein byreference. In addition, a compound described in JP2016-146619A can alsobe used as the near infrared absorber, the content of which isincorporated herein by reference. Specific examples of the organiccompound used as the near infrared absorber include a compound describedin Examples described below. In addition, as the rylene compound, forexample, a compound having the following structure can also be used. Inthe following structural formula, R's each independently represent ahydrogen atom, a linear or branched alkyl group having 1 to 22 carbonatoms, an acyl group, or a group represented by the following Formula(1).

In Formula (1), R¹ represents a linear or branched alkyl group having 1to 22 carbon atoms.

Examples of the pyrrolopyrrole compound include a compound representedby Formula (PP).

In the formula, R^(1a) and R^(1b) each independently represent an alkylgroup, an aryl group, or a heteroaryl group, R² and R³ eachindependently represent a hydrogen atom or a substituent, R² and R³ maybe bonded to each other to form a ring, R⁴'s each independentlyrepresent a hydrogen atom, an alkyl group, an aryl group, a heteroarylgroup, —BR^(4A)R^(4B), or a metal atom, R⁴ may form a covalent bond or acoordinate bond with at least one selected from R^(1a), R^(1b), or R³,and R^(4A) and R^(4B) each independently represent a substituent. R^(4A)and R^(4B) may be bonded to each other to form a ring. The details ofFormula (PP) can be found in paragraphs “0017” to “0047” ofJP2009-263614A, paragraphs “0011” to “0036” of JP2011-068731A, andparagraphs “0010” to “0024” of WO2015/166873A, the contents of which areincorporated herein by reference.

In Formula (PP), R^(1a) and R^(1b) each independently representpreferably an aryl group or a heteroaryl group, and more preferably anaryl group. In addition, the alkyl group, the aryl group, and theheteroaryl group represented by R^(1a) and R^(1b) may have a substituentor may be unsubstituted. Examples of the substituent includesubstituents described in paragraphs “0020” to “0022” of 2009-0263614Aand the following substituent T.

(Substituent T)

The substituent T includes an alkyl group (preferably an alkyl grouphaving 1 to 30 carbon atoms), an alkenyl group (preferably an alkenylgroup having 2 to 30 carbon atoms), an alkynyl group (preferably analkynyl group having 2 to 30 carbon atoms), an aryl group (preferably anaryl group having 6 to 30 carbon atoms), an amino group (preferably anamino group having 0 to 30 carbon atoms), an alkoxy group (preferably analkoxy group having 1 to 30 carbon atoms), an aryloxy group (preferablyan aryloxy group having 6 to 30 carbon atoms), a heteroaryloxy group, anacyl group (preferably having an acyl group 1 to 30 carbon atoms), analkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 30carbon atoms), an aryloxycarbonyl group (preferably an aryloxycarbonylgroup having 7 to 30 carbon atoms), an acyloxy group (preferably anacyloxy group having 2 to 30 carbon atoms), an acylamino group(preferably an acylamino group having 2 to 30 carbon atoms), analkoxycarbonylamino group (preferably an alkoxycarbonylamino grouphaving 2 to 30 carbon atoms), an aryloxycarbonylamino group (preferablyan aryloxycarbonylamino group having 7 to 30 carbon atoms), a sulfamoylgroup (preferably a sulfamoyl group having 0 to 30 carbon atoms), acarbamoyl group (preferably a carbamoyl group having 1 to 30 carbonatoms), an alkylthio group (preferably an alkylthio group having 1 to 30carbon atoms), an arylthio group (preferably an arylthio group having 6to 30 carbon atoms), a heteroarylthio group (preferably having 1 to 30carbon atoms), an alkylsulfonyl group (preferably having 1 to 30 carbonatoms), an arylsulfonyl group (preferably having 6 to 30 carbon atoms),a heteroarylsulfonyl group (preferably having 1 to 30 carbon atoms), analkylsulfinyl group (preferably having 1 to 30 carbon atoms), anarylsulfinyl group (preferably having 6 to 30 carbon atoms), aheteroarylsulfinyl group (preferably having 1 to 30 carbon atoms), aureido group (preferably having 1 to 30 carbon atoms), a hydroxy group,a carboxyl group, a sulfo group, a phosphate group, a carboxylic acidamide group, a sulfonic acid amide group, an imide acid group, amercapto group, a halogen atom, a cyano group, an alkylsulfino group, anarylsulfino group, a hydrazino group, an imino group, and a heteroarylgroup (preferably having 1 to 30 carbon atoms). In a case where theabove-described groups can be further substituted, the groups mayfurther have a substituent. Examples of the substituent include thegroups described regarding the substituent T.

Specific examples of the group represented by R^(1a) and R^(1b) includean aryl group which has an alkoxy group as a substituent, an aryl groupwhich has a hydroxy group as a substituent, and an aryl group which hasan acyloxy group as a substituent.

In Formula (PP), R² and R³ each independently represent a hydrogen atomor a substituent. Examples of the substituent include theabove-described substituent T. It is preferable that at least one of R²or R³ represents an electron-withdrawing group. A substituent having apositive Hammett's substituent constant σ value (sigma value) acts as anelectron-withdrawing group. Here, the substituent constant obtained byHammett's rule includes a σp value and a σm value. The values can befound in many common books. In the present invention, a substituenthaving the Hammett's substituent constant σ value of 0.2 or more can beexemplified as the electron-withdrawing group. σ value is preferably0.25 or more, more preferably 0.3 or more, and still more preferably0.35 or more. The upper limit is not particularly limited, butpreferably 0.80 or less. Specific examples of the electron-withdrawinggroup include a cyano group (σp value=0.66), a carboxyl group (—COOH: σpvalue=0.45), an alkoxycarbonyl group (for example, —COOMe: σpvalue=0.45), an aryloxycarbonyl group (for example, —COOPh: σpvalue=0.44), a carbamoyl group (for example, —CONH₂: σp value=0.36), analkylcarbonyl group (for example, —COMe: σp value=0.50), an arylcarbonylgroup (for example, —COPh: σp value=0.43), an alkylsulfonyl group (forexample, —SO₂Me: σp value=0.72), and an arylsulfonyl group (for example,—SO₂Ph: σp value=0.68). Among these, a cyano group is preferable. Here,Me represents a methyl group, and Ph represents a phenyl group. Forexample, the Hammett's substituent constant σ value can be found in thedescription of paragraphs “0017” and “0018” of JP2011-068731A, thecontent of which is incorporated herein by reference.

In Formula (PP), it is preferable that R² represents anelectron-withdrawing group (preferably a cyano group) and R³ representsa heteroaryl group. It is preferable that the heteroaryl group is a 5-or 6-membered ring. In addition, the heteroaryl group is preferably amonocyclic or fused ring, more preferably a monocyclic or fused ringincluding 2 to 8 rings, and still more preferably a monocyclic or fusedring including 2 to 4 rings. The number of heteroatoms forming theheteroaryl group is preferably 1 to 3 and more preferably 1 or 2.Examples of the heteroatom include a nitrogen atom, an oxygen atom, anda sulfur atom. It is preferable that the heteroaryl group has one ormore nitrogen atoms. Two R²'s in Formula (PP) may be the same as ordifferent from each other. In addition, two R³'s in Formula (PP) may bethe same as or different from each other.

In Formula (PP), R⁴ represents preferably a hydrogen atom, an alkylgroup, an aryl group, a heteroaryl group, or a group represented by—BR^(4A)R^(4B), more preferably a hydrogen atom, an alkyl group, an arylgroup, or a group represented by —BR^(4A)R^(4B), and still morepreferably a group represented by —BR^(4A)R^(4B). As the substituentrepresented by R^(4A) and R^(4B), a halogen atom, an alkyl group, analkoxy group, an aryl group, or a heteroaryl group is preferable, analkyl group, an aryl group, or a heteroaryl group is more preferable,and an aryl group is still more preferable. Each of the groups mayfurther have a substituent. Two R⁴'s in Formula (PP) may be the same asor different from each other. R^(4A) and R^(4B) may be bonded to eachother to form a ring.

Specific examples of the pyrrolopyrrole compound include a compounddescribed in Examples described below. In addition, Examples of thepyrrolopyrrole compound include compounds described in paragraphs “0016”to “0058” of JP2009-263614A, compounds described in paragraphs “0037” to“0052” of JP2011-068731A, compounds described in paragraphs “0010” to“0033” of WO2015/166873A, the contents of which are incorporated hereinby reference.

It is preferable that the squarylium compound is a compound representedby the following Formula (SQ1).

In the formulae, As¹ and As² each independently represent an aryl group,a heterocyclic group, or a group represented by Formula (As-1).

In the formula, * represents a direct bond.

Rs¹ to Rs³ each independently represent a hydrogen atom or an alkylgroup.

As³ represents a heterocyclic group.

n_(s1) represents an integer of 0 or more.

Rs¹ and Rs² may be bonded to each other to form a ring.

Rs¹ and As³ may be bonded to each other to form a ring.

Rs² and Rs³ may be bonded to each other to form a ring.

In a case where n_(s1) represents 2 or more, a plurality of Rs²'s may bethe same as or different from each other and a plurality of Rs³'s may bethe same as or different from each other.

The number of carbon atoms in the aryl group represented by As¹ and As²is preferably 6 to 48, more preferably 6 to 22, and still morepreferably 6 to 12.

It is preferable that the heterocyclic group represented by As¹, As²,and As³ is a 5- or 6-membered heterocyclic group. In addition, theheterocyclic group is preferably a monocyclic or fused heterocyclicgroup including 2 to 8 rings, more preferably a monocyclic or fusedheterocyclic group including 2 to 4 rings, still more preferably amonocyclic or fused heterocyclic group including 2 or 3 rings, and stillmore preferably a monocyclic or fused heterocyclic group including 2rings. Examples of a heteroatom included in the ring of the heterocyclicgroup include a nitrogen atom, an oxygen atom, and a sulfur atom. Amongthese, a nitrogen atom or a sulfur atom is preferable. The number ofheteroatoms forming the ring of the heterocyclic group is preferably 1to 3 and more preferably 1 or 2.

Rs¹ to Rs³ in Formula (As-1) each independently represent a hydrogenatom or an alkyl group. The number of carbon atoms in the alkyl grouprepresented by Rs¹ to Rs³ is preferably 1 to 20, more preferably 1 to15, and still more preferably 1 to 8. The alkyl group may be linear,branched, or cyclic and is preferably linear or branched. It ispreferable that Rs¹ to Rs³ represent a hydrogen atom.

n_(s1) in Formula (As-1) represents an integer of 0 or more. n_(s1)represents preferably an integer of 0 to 2, more preferably 0 or 1, andstill more preferably 0.

In Formula (As-1), Rs¹ and Rs² may be bonded to each other to form aring, Rs¹ and As³ may be bonded to each other to form a ring, and Rs²and Rs³ may be bonded to each other to form a ring. It is preferablethat a linking group for forming the ring is a divalent linking groupselected from the group consisting of —CO—, —O—, —NH—, an alkylene grouphaving 1 to 10 carbon atoms, and a combination thereof. The alkylenegroup as the linking group may be unsubstituted or may have asubstituent. Examples of the substituent include the above-describedsubstituent T.

In Formula (SQ1), it is preferable that the group represented by As¹ andAs² has a substituent. Examples of the substituent include theabove-described substituent T.

In Formula (SQ1), it is preferable that As¹ and As² each independentlyrepresent an aryl group or a heterocyclic group, or it is preferablethat As¹ and As² each independently represent a group represented byFormula (As-1).

As shown below, cations in Formula (SQ1) are present without beinglocalized.

It is preferable that the squarylium compound is a compound representedby the following Formula (SQ2) or a compound represented by thefollowing Formula (SQ3).

Rs¹¹ and Rs¹² each independently represent a hydrogen atom or asubstituent.

Rs¹³ and Rs¹ each independently represent a substituent.

n_(s11) and n_(s12) each independently represent an integer of 0 to 3.

In a case where n_(s11) represents 2 or more, two Rs¹³'s may be bondedto each other to form a ring.

In a case where n_(s12) represents 2 or more, two Rs¹³'s may be bondedto each other to form a ring.

Rs²¹ to Rs²⁴ each independently represent an alkyl group, an aryl group,or a heteroaryl group.

Rs²¹ and Rs²², Rs²³ and Rs²⁴, Rs²¹ and Rs¹³, Rs²² and Rs¹³, Rs²³ andRs¹⁴, Rs²⁴ and Rs¹⁴, Rs²¹ and a ring two Rs¹³'s formed by being bondedto each other, or Rs²³ and a ring formed by two Rs¹⁴'s being bonded toeach other may be bonded to each other to form a ring.

As the substituent represented by Rs¹¹ and Rs¹² in Formula (SQ2), agroup having active hydrogen is preferable, —OH, —SH, —COOH, —SO₃H,—NR^(X1)R^(X2), —NHCOR^(X1), —CONR^(X1)R^(X2), —NHCONR^(X1)R^(X2),—NHCOOR^(X1), —NHSO₂R^(X1), —B(OH)₂, or —PO(OH)₂ is more preferable, and—OH, —SH, or —NR^(X1)R^(X2) is still more preferable. R^(X1) and R^(X2)each independently represent a hydrogen atom or a substituent. Examplesof the substituent R^(X1) and R^(X2) include an alkyl group, an arylgroup, and a heteroaryl group. Among these, an alkyl group ispreferable.

Examples of the substituent represented by Rs¹³ and Rs¹⁴ in Formula(SQ2) include the above-described substituent T.

In Formula (SQ2), Rs²¹ to Rs²⁴ each independently represent an alkylgroup, an aryl group, or a heteroaryl group. The number of carbon atomsin the alkyl group is preferably 1 to 20, more preferably 1 to 15, andstill more preferably 1 to 8. The alkyl group may be linear, branched,or cyclic and is preferably linear or branched. The number of carbonatoms in the aryl group is preferably 6 to 30, more preferably 6 to 20,and still more preferably 6 to 12. The heteroaryl group is preferably amonocyclic or fused heteroaryl group including 2 to 8 rings, and morepreferably a monocyclic or fused heteroaryl group including 2 to 4rings. The number of heteroatoms forming the ring of the heteroarylgroup is preferably 1 to 3. It is preferable that the heteroatomsforming the ring of the heteroaryl group are a nitrogen atom, an oxygenatom, or a sulfur atom. It is preferable that the heteroaryl group is a5- or 6-membered ring. The number of carbon atoms forming the ring ofthe heteroaryl group is preferably 3 to 30, more preferably 3 to 18, andstill more preferably 3 to 12. The alkyl group, the aryl group, and theheteroaryl group may have a substituent or may be unsubstituted.Examples of the substituent include the substituents described aboveregarding the substituent T.

In Formula (SQ2), n_(s11) and n_(s12) each independently represent aninteger of 0 to 3 and preferably an integer of 0 to 2.

In Formula (SQ2), in a case where n_(s11) represents 2 or more, twoRs¹³'s may be bonded each other to form a ring. In a case where n_(s12)represents 2 or more, two Rs¹⁴'s may be bonded to each other to form aring. It is preferable that a linking group for forming the ring is adivalent linking group selected from the group consisting of —CO—, —O—,—NH—, an alkylene group having 1 to 10 carbon atoms, and a combinationthereof. The alkylene group as the linking group may be unsubstituted ormay have a substituent. Examples of the substituent include theabove-described substituent T.

In Formula (SQ2), Rs²¹ and Rs²², Rs²³ and Rs²⁴, Rs²¹ and Rs¹³, Rs²² andRs¹³, Rs²³ and Rs¹⁴, or Rs²⁴ and Rs¹⁴ may be bonded to each other toform a ring. In addition, in a case where two Rs¹³'s are bonded to eachother to form a ring, Rs²¹ and a ring formed by two Rs¹³'s being bondedto each other may be further bonded to each other to form a ring. Inaddition, in a case where two Rs¹⁴'s are bonded to each other to form aring, Rs²³ and a ring formed by two Rs¹⁴'s being bonded to each othermay be further bonded to each other to form a ring. It is preferablethat a linking group for forming the ring is a divalent linking groupselected from the group consisting of —CO—, —O—, —NH—, an alkylene grouphaving 1 to 10 carbon atoms, and a combination thereof. The alkylenegroup as the linking group may be unsubstituted or may have asubstituent. Examples of the substituent include the above-describedsubstituent T. In a case where Rs²¹ and a ring formed by two Rs¹³'sbeing bonded to each other are further bonded to each other to form aring, the ring has, for example, the following structure. In thefollowing formula, A1 represents a ring formed by two Rs¹³'s beingbonded to each other, A2 represents a ring formed by the ring A1 andRs²² being bonded to each other, Rs²² represents an alkyl group, an arylgroup, or a heteroaryl group, Rs¹¹ and Rs¹³ represent a hydrogen atom ora substituent, and * represents a direct bond. The same can be appliedto a case where Rs²³ and a ring formed by two Rs¹⁴'s being bonded toeach other are further bonded to each other to form a ring.

Specific examples of the squarylium compound include compounds describedin Examples described below. In addition, examples of the squaryliumcompound include a compound described in paragraphs “0044” to “0049” ofJP2011-208101A, a compound described in paragraphs “0060” and “0061” ofJP6065169B, a compound described in paragraph “0040” of WO2016/181987A,a compound described in WO2013/133099A, a compound described inWO2014/088063A, a compound described in JP2014-126642A, a compounddescribed in JP2016-146619A, a compound described in JP2015-176046A, acompound described in JP2017-025311A, a compound described inWO2016/154782A, a compound described in JP5884953B, a compound describedin JP6036689B, a compound described in JP5810604B, and a compounddescribed in JP2017-068120A, the contents of which are incorporatedherein by reference.

As the cyanine compound, a compound represented by Formula (Cy1) ispreferable.

Rcy¹ to Rcy⁵ each independently represent a hydrogen atom or asubstituent, and two of Rcy¹ to Rcy⁵ may be bonded to each other to forma ring. n_(cy1) represents an integer of 0 to 2, and in a case wheren_(cy1) represents 2, a plurality of Rcy⁴'s and a plurality of Rcy⁵'smay be the same as or different from each other, respectively. Acy¹ andAcy² each independently represent an aryl group or a heterocyclic group.In a case where a site represented by Cy in the formula is a cationsite, Y represents a counter anion, and c represents the number of Y'sfor balancing charge. In a case where a site represented by Cy in theformula is an anion site, Y represents a counter cation, and crepresents the number of Y's for balancing charge. In a case wherecharge of a site represented by Cy in the formula is neutralized in amolecule, c represents 0.

Rcy¹ to Rcy⁵ each independently represent a hydrogen atom or asubstituent. Examples of the substituent include the above-describedsubstituent T. In Formula (Cy1), two of Rcy¹ to Rcy⁵ may be bonded toeach other to form a ring. It is preferable that a linking group forforming the ring is a divalent linking group selected from the groupconsisting of —CO—, —O—, —NH—, an alkylene group having 1 to 10 carbonatoms, and a combination thereof. The alkylene group as the linkinggroup may be unsubstituted or may have a substituent. Examples of thesubstituent include the above-described substituent T.

n_(cy1) represents an integer of 0 to 2 and preferably 0 or 1. In a casewhere n_(cy1) represents 2, a plurality of Rcy⁴'s may be the same as ordifferent from each other and a plurality of Rcy⁵'s may be the same asor different from each other.

The number of carbon atoms in the aryl group represented by Acy¹ andAcy² is preferably 6 to 48, more preferably 6 to 22, and still morepreferably 6 to 12. It is preferable that the heterocyclic grouprepresented by Acy¹ and Acy² is a 5- or 6-membered heterocyclic group.In addition, the heterocycle is preferably a monocyclic or fusedheterocyclic group including 2 to 8 rings, more preferably a monocyclicor fused heterocyclic group including 2 to 4 rings, still morepreferably a monocyclic or fused heterocyclic group including 2 or 3rings, and still more preferably a monocyclic or fused heterocyclicgroup including 2 rings. Examples of a heteroatom included in the ringof the heterocyclic group include a nitrogen atom, an oxygen atom, and asulfur atom. Among these, an oxygen atom or a sulfur atom is preferable.The number of heteroatoms forming the ring of the heterocyclic group ispreferably 1 to 3 and more preferably 1 or 2. The group represented byAcy¹ and Acy² may have a substituent. Examples of the substituentinclude the above-described substituent T.

In a case where a site represented by Cy in Formula (Cy1) is a cationsite, Y represents a counter anion, and c represents the number of Y'sfor balancing charge. Examples of the counter anion include a halogenion (Cl⁻, Br⁻, I⁻), a p-toluenesulfonate ion, an ethyl sulfate ion, PF₆⁻, BF₄ ⁻ or ClO₄ ⁻, a tris(halogenoalkylsulfonyl)methide anion (forexample, (CF₃SO₂)₃C⁻), a di(halogenoalkylsulfonyl)imide anion (forexample, (CF₃SO₂)₂N⁻), and a tetracyanoborate anion.

In a case where a site represented by Cy in Formula (Cy1) is an anionsite, Y represents a counter cation, and c represents the number of Y'sfor balancing charge. Examples of the counter cation include an alkalimetal ion (for example, Li⁺, Na⁺, or K⁺), an alkali earth metal ion(Mg²⁺, Ca²⁺, Ba²⁺, or Sr²⁺), a transition metal ion (for example, Ag⁺,Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, or Zn²⁺), other metal ions (for example, Al³⁺),an ammonium ion, a triethylammonium ion, a tributylammonium ion, apyridinium ion, a tetrabutylammonium ion, a guanidinium ion, atetramethylguanidinium ion, and a diazabicycloundecenium ion.

In a case where charge of a site represented by Cy in Formula (Cy1) isneutralized in a molecule, Y is not present. That is, c represents 0.

Specific examples of the cyanine compound include compounds described inExamples described below. In addition, examples of the cyanine compoundinclude a compound described in paragraphs “0044” and “0045” ofJP2009-108267A, a compound described in paragraphs “0026” to “0030” ofJP2002-194040, a compound described in JP2015-172004A, a compounddescribed in JP2015-172102A, a compound described in JP2008-088426A, anda compound described in JP2017-031394A, the contents of which areincorporated herein by reference.

(Croconium Compound)

It is preferable that the croconium compound is a compound representedby the following Formula (Cr1).

In the formulae, Ac¹ and Ac² each independently represent an aryl group,a heterocyclic group, or a group represented by Formula (Ac-1).

In the formula, * represents a direct bond.

Rc¹ to Rc³ each independently represent a hydrogen atom or an alkylgroup.

Ac³ represents a heterocyclic group.

n_(c1) represents an integer of 0 or more.

Rc¹ and Rc² may be bonded to each other to form a ring.

Rc¹ and Ac³ may be bonded to each other to form a ring.

Rc² and Rc³ may be bonded to each other to form a ring.

In a case where n_(c1) represents 2 or more, a plurality of Rc²'s may bethe same as or different from each other and a plurality of Rc³'s may bethe same as or different from each other.

The number of carbon atoms in the aryl group represented by Ac¹ and Ac²is preferably 6 to 48, more preferably 6 to 22, and still morepreferably 6 to 12.

It is preferable that the heterocyclic group represented by Ac¹, Ac²,and Ac³ is a 5- or 6-membered heterocyclic group. In addition, theheterocycle is preferably a monocyclic or fused heterocyclic groupincluding 2 to 8 rings, more preferably a monocyclic or fusedheterocyclic group including 2 to 4 rings, still more preferably amonocyclic or fused heterocyclic group including 2 or 3 rings, and stillmore preferably a monocyclic or fused heterocyclic group including 2rings. Examples of a heteroatom included in the ring of the heterocyclicgroup include a nitrogen atom, an oxygen atom, and a sulfur atom. Amongthese, a nitrogen atom or a sulfur atom is preferable. The number ofheteroatoms forming the ring of the heterocyclic group is preferably 1to 3 and more preferably 1 or 2.

Rc¹ to Rc³ in Formula (Ac-1) each independently represent a hydrogenatom or an alkyl group. The number of carbon atoms in the alkyl grouprepresented by Rc¹ to Rc³ is preferably 1 to 20, more preferably 1 to15, and still more preferably 1 to 8. The alkyl group may be linear,branched, or cyclic and is preferably linear or branched. It ispreferable that Rc¹ to Rc³ represent a hydrogen atom.

n_(c1) in Formula (Ac-1) represents an integer of 0 or more. n_(c1)represents preferably an integer of 0 to 2, more preferably 0 or 1, andstill more preferably 1.

In Formula (Ac-1), Rc¹ and Rc² may be bonded to each other to form aring, Rc¹ and Ac³ may be bonded to each other to form a ring, and Rc²and Rc³ may be bonded to each other to form a ring. It is preferablethat a linking group for forming the ring is a divalent linking groupselected from the group consisting of —CO—, —O—, —NH—, an alkylene grouphaving 1 to 10 carbon atoms, and a combination thereof. The alkylenegroup as the linking group may be unsubstituted or may have asubstituent. Examples of the substituent include the above-describedsubstituent T.

In Formula (Cr1), it is preferable that the group represented by Ac¹ andAc² has a substituent. Examples of the substituent include theabove-described substituent T.

In Formula (Cr1), it is preferable that Ac¹ and Ac² each independentlyrepresent an aryl group or a heterocyclic group, or it is preferablethat Ac¹ and Ac² each independently represent a group represented byFormula (Ac-1).

As shown below, cations in Formula (Cr1) are present without beinglocalized.

Specific examples of the croconium compound include a compound describedbelow in Examples. In addition, examples of the croconium compoundinclude a compound described in JP1993-155145A (JP-H5-155145A) and acompound described in JP2007-031644A, the contents of which areincorporated herein by reference.

It is preferable that the iminium compound is a compound represented bythe following Formula (Im).

In the formula, R¹¹ to R¹⁸ each independently represent an alkyl groupor an aryl group, V¹¹ to V¹⁵ each independently represent an alkylgroup, an aryl group, a halogen atom, an alkoxy group, or a cyano group,X represents a counter anion, c represents the number of X's forbalancing charge, and n1 to n5 each independently 0 to 4.

R¹¹ to R¹⁸ each independently represent an alkyl group or an aryl group.The number of carbon atoms in the alkyl group is preferably 1 to 20,more preferably 1 to 12, and still more preferably 1 to 8. The alkylgroup may be linear, branched, or cyclic and is preferably linear orbranched. The number of carbon atoms in the aryl group is preferably 6to 25, more preferably 6 to 15, and still more preferably 6 to 12. Thealkyl group and the aryl group may have a substituent or may beunsubstituted. Examples of the substituent include the groups describedregarding the substituent T.

V¹¹ to V¹⁵ each independently represent an alkyl group, an aryl group, ahalogen atom, an alkoxy group, or a cyano group. Examples of the halogenatom include a fluorine atom, a chlorine atom, a bromine atom, and aniodine atom. The number of carbon atoms in the alkyl group is preferably1 to 20, more preferably 1 to 12, and still more preferably 1 to 8. Thealkyl group may be linear, branched, or cyclic and is preferably linearor branched and more preferably linear. The number of carbon atoms inthe aryl group is preferably 6 to 25, more preferably 6 to 15, and stillmore preferably 6 to 12. The number of carbon atoms in the alkoxy groupis preferably 1 to 20, more preferably 1 to 12, and still morepreferably 1 to 8. The alkoxy group may be linear, branched, or cyclicand is preferably linear or branched and more preferably linear.

n1 to n5 each independently 0 to 4. n1 to n4 represents preferably 0 to2 and more preferably 0 or 1. n5 represents preferably 0 to 3 and morepreferably 0 to 2.

X represents a counter anion. Examples of the counter anion include ahalogen ion (Cl⁻, Br⁻, I⁻), a p-toluenesulfonate ion, an ethyl sulfateion, PF₆ ⁻, BF₄ ⁻ or ClO₄ ⁻, a tris(halogenoalkylsulfonyl)methide anion(for example, (CF₃SO₂)₃C⁻), a di(halogenoalkylsulfonyl)imide anion (forexample, (CF₃SO₂)₂N⁻), and a tetracyanoborate anion.

c represents the number of X's for balancing charge, for example,preferably 2.

Examples of the iminium compound include a compound described inJP2008-528706A, a compound described in JP2012-012399A, and a compounddescribed in JP2007-092060A, the contents of which are incorporatedherein by reference.

As the near infrared absorber, a commercially available product can alsobe used. Examples of a commercially available product of the nearinfrared absorber include SDO-C33 (manufactured by Arimoto Chemical Co.,Ltd.); EXCOLOR IR-14, EXCOLOR IR-10A, EXCOLOR TX-EX-801B, and EXCOLORTX-EX-805K (manufactured by Nippon Shokubai Co., Ltd.); ShigenoxNIA-8041, Shigenox NIA-8042, Shigenox NIA-814, Shigenox NIA-820, andShigenox NIA-839 (manufactured by Hakkol Chemical Co., Ltd.); EpoliteV-63, Epolight 3801, and Epolight3036 (manufactured by Epolin Inc.);PRO-JET 825LDI (manufactured by Fujifilm Corporation); NK-3027 andNK-5060 (manufactured by Hayashibara Co., Ltd.); and YKR-3070(manufactured by Mitsui Chemicals, Inc.).

The content of the near infrared absorber is preferably 3 mass % orhigher, more preferably 5 mass % or higher, still more preferably 8 mass% or higher, still more preferably 10 mass % or higher, still morepreferably 15 mass % or higher, and still more preferably 20 mass % orhigher with respect to the total solid content of the photosensitivecomposition. The upper limit is preferably 60 mass % or lower, morepreferably 55 mass % or lower, still more preferably 50 mass % or lower,still more preferably 45 mass % or lower, and still more preferably 40mass % or lower.

In addition, In a case where the photosensitive composition according tothe embodiment of the present invention is used as a photosensitivecomposition for a near infrared cut filter, from the viewpoints of thethickness of a film used and near infrared blocking properties, thecontent of the near infrared absorber is preferably 5 mass % or higher,more preferably 10 mass % or higher, still more preferably 15 mass % orhigher, and still more preferably 20 mass % or higher with respect tothe total solid content of the photosensitive composition. From theviewpoint of pattern formability, the upper limit is preferably 60 mass% or lower, more preferably 55 mass % or lower, and still morepreferably 50 mass % or lower.

In addition, in a case where the photosensitive composition according tothe embodiment of the present invention is used as a photosensitivecomposition for a near infrared transmitting filter, from the viewpointsof the thickness of a film used and near infrared blocking properties,the content of the near infrared absorber is preferably 3 mass % orhigher, more preferably 5 mass % or higher, still more preferably 8 mass% or higher, still more preferably 10 mass % or higher, still morepreferably 15 mass % or higher with respect to the total solid contentof the photosensitive composition. From the viewpoint of patternformability, the upper limit is preferably 50 mass % or lower, morepreferably 45 mass % or lower, and still more preferably 40 mass % orlower.

In the present invention, as the near infrared absorber one kind may beused alone, or two or more kinds may be used. In a case where two ormore near infrared absorbers are used, it is preferable that the totalcontent of the two or more near infrared absorbers is in theabove-described range.

(Coloring Material that Allows Transmission of Near Infrared Light andBlocks Visible Light)

The curable composition according to the embodiment of the presentinvention may also include the coloring material that allowstransmission of near infrared light and blocks visible light(hereinafter, also referred to as “coloring material that blocks visiblelight”).

In the present invention, it is preferable that the coloring materialthat blocks visible light is a coloring material that absorbs light in awavelength range of violet to red. In addition, in the presentinvention, it is preferable that the coloring material that blocksvisible light is a coloring material that blocks light in a wavelengthrange of 450 to 650 nm. In addition, it is preferable that the coloringmaterial that blocks visible light is a coloring material that allowstransmission of light in a wavelength range of 900 to 1300 nm.

In the present invention, it is preferable that the coloring materialthat blocks visible light satisfies at least one of the followingrequirement (1) or (2).

(1): The coloring material that blocks visible light includes two ormore chromatic colorants, and a combination of the two or more chromaticcolorants forms black.

(2): The coloring material includes an organic black colorant.

Examples of the chromatic colorant include a red colorant, a greencolorant, a blue colorant, a yellow colorant, a violet colorant, and anorange colorant. As the chromatic colorant, a pigment or a dye may beused. It is preferable that the chromatic colorant is a pigment. Anaverage particle size (r) of the pigment satisfies preferably 20nm≤r≤300 nm, more preferably 25 nm≤r≤250 nm, and still more preferably30 nm≤r≤200 nm. “Average particle size” described herein denotes theaverage particle size of secondary particles which are aggregates ofprimary particles of the pigment. In addition, regarding a particle sizedistribution of the secondary particles of the pigment (hereinafter,simply referred to as “particle size distribution”) which can be used,secondary particles having a particle size of (average particlesize±100) nm account for preferably 70 mass % or higher and morepreferably 80 mass % or higher in the pigment.

As the pigment, an organic pigment is preferable. Preferable examples ofthe organic pigment are as follows:

Color Index (C.I.) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14,15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40,42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95,97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118,119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150,151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170,171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188,193, 194, 199, 213, and 214 (all of which are yellow pigments);

C.I. Pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49,51, 52, 55, 59, 60, 61, 62, 64, 71, and 73 (all of which are orangepigments);

C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41,48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1,63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123,144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177,178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210,216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, and 279 (all ofwhich are red pigments);

C.I. Pigment Green 7, 10, 36, 37, 58, 59, 62, and 63 (all of which aregreen pigments);

C.I. Pigment Violet 1, 19, 23, 27, 32, 37, and 42 (all of which areviolet pigments);

and

C.I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60,64, 66, 79, and 80 (all of which are blue pigments).

Among these organic pigments, one kind may be used alone, or two or morekinds may be used in combination.

In addition, as the yellow pigment, a metal azo pigment including atleast one anion selected from an azo compound represented by thefollowing Formula (I) or an azo compound having a tautomeric structureof the azo compound represented by Formula (I), two or more metal ions,and a melamine compound can be used.

In the formula, R¹ and R² each independently represent OH or NR⁵R⁶, R³and R⁴ each independently represent ═O or ═NR⁷, and R⁵ to R⁷ eachindependently represent a hydrogen atom or an alkyl group. The number ofcarbon atoms in the alkyl group represented by R⁵ to R⁷ is preferably 1to 10, more preferably 1 to 6, and still more preferably 1 to 4. Thealkyl group may be linear, branched, or cyclic and is preferably linearor branched and more preferably linear. The alkyl group may have asubstituent. As the substituent, a halogen atom, a hydroxy group, analkoxy group, a cyano group, or an amino group is preferable.

In Formula (I), it is preferable that R¹ and R² represent OH. Inaddition, it is preferable that R³ and R⁴ represent O.

It is preferable that the melamine compound in the metal azo pigment isa compound represented by the following Formula (II).

In the formula, R¹¹ to R¹³ each independently represent a hydrogen atomor an alkyl group. The number of carbon atoms in the alkyl group ispreferably 1 to 10, more preferably 1 to 6, and still more preferably 1to 4. The alkyl group may be linear, branched, or cyclic and ispreferably linear or branched and more preferably linear. The alkylgroup may have a substituent. As the substituent, a hydroxy group ispreferable. It is preferable that at least one of R¹¹, . . . , or R¹³represents a hydrogen atom, and it is more preferable that all of R¹¹ toR¹³ represent a hydrogen atom.

It is preferable that the above-described metal azo pigment is a metalazo pigment according to an aspect including at least one anion selectedfrom an azo compound represented by Formula (I) or an azo compoundhaving a tautomeric structure of the azo compound represented by Formula(I), metal ions including at least Zn²⁺ and Cu²⁺, and a melaminecompound. In this aspect, the total content of Zn²⁺ and Cu²⁺ ispreferably 95 to 100 mol %, more preferably 98 to 100 mol %, still morepreferably 99.9 to 100 mol %, and still more preferably 100 mol % withrespect to 1 mol of all the metal ions of the metal azo pigment. Inaddition, a molar ratio Zn²⁺:Cu²⁺ of Zn²⁺ to Cu²⁺ in the metal azopigment is preferably 199:1 to 1:15, more preferably 19:1 to 1:1, andstill more preferably 9:1 to 2:1. In addition, in this aspect, the metalazo pigment may further include a divalent or trivalent metal ion(hereinafter, also referred to as “metal ion Me1”) in addition to Zn²⁺and Cu²⁺. Examples of the metal ion Me1 include Ni²⁺, Al³⁺, Fe²⁺, Fe³⁺,Co²⁺, Co³⁺, La³⁺, Ce³⁺, Pr³⁺, Nd²⁺, Nd³⁺, Sm²⁺, Sm³⁺, Eu²⁺, Eu³⁺, Gd³⁺,Tb³⁺, Dy³⁺, Ho³⁺, Yb²⁺, Yb³⁺, Er³⁺, Tm³⁺, Mg²⁺, Ca²⁺, Sr²⁺, Mn²⁺, Y³⁺,Sc³⁺, Ti²⁺, Ti³⁺, Nb³⁺, Mo²⁺, Mo³⁺, V²⁺, V³⁺, Zr²⁺, Zr³⁺, Cd²⁺, Cr³⁺,Pb²⁺, and Ba²⁺. Among these, at least one selected from Al³⁺, Fe²⁺,Fe³⁺, Co²⁺, Co³⁺, La³⁺, Ce³⁺, Pr³⁺, Nd³⁺, Sm³⁺, Eu³⁺, Gd³⁺, Tb³⁺, Dy³⁺,Ho³⁺, Yb³⁺, Er³⁺, Tm³⁺, Mg²⁺, Ca²⁺, Sr²⁺, Mn²⁺, or Y³⁺ is preferable, atleast one selected from Al³⁺, Fe²⁺, Fe³⁺, Co²⁺, Co³⁺, La³⁺, Ce³⁺, Pr³⁺,Nd³⁺, Sm³⁺, Tb³⁺, Ho³⁺, or Sr²⁺ is more preferable, and at least oneselected from Al³⁺, Fe²⁺, Fe³⁺, Co²⁺, or Co³⁺ is still more preferable.The content of the metal ion Me1 is preferably 5 mol % or lower, morepreferably 2 mol % or lower, and still more preferably 0.1 mol % orlower with respect to 1 mol of all the metal ions of the metal azopigment.

The details of the metal azo pigment can be found in paragraphs “0011”to “0062” and “0137” to “0276” of JP2017-171912A, paragraphs “0010” to“0062” and “0138” to “0295” of JP2017-171913A, paragraphs “0011” to“0062” and “0139” to “0190” of JP2017-171914A, and paragraphs “0010” to“0065” and “0142” to “0222” of JP2017-171915A, the contents of which areincorporated herein by reference.

In addition, as the red pigment, a compound having a structure in whichan aromatic ring group into which a group having an oxygen atom, asulfur atom, or a nitrogen atom bonded to an aromatic ring is introducedis bonded to a diketo pyrrolo pyrrole skeleton can also be used. Thiscompound is preferably a compound represented by Formula (DPP1) and morepreferably a compound represented by Formula (DPP2).

In the formula, R11 and R13 each independently represent a substituent,R¹² and R¹⁴ each independently represent a hydrogen atom, an alkylgroup, an aryl group, or a heteroaryl group, n11 and n13 eachindependently represent an integer of 0 to 4, X¹² and X¹⁴ eachindependently represent an oxygen atom, a sulfur atom, or a nitrogenatom, in a case where X¹² represents an oxygen atom or a sulfur atom,m12 represents 1, in a case where X¹² represents a nitrogen atom, m12represents 2, in a case where X¹⁴ represents an oxygen atom or a sulfuratom, m14 represents 1, and in a case where X¹⁴ represents a nitrogenatom, m14 represents 2. Specific preferable example of the substituentrepresented by R¹¹ and R¹³ include an alkyl group, an aryl group, ahalogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonylgroup, a heteroaryloxycarbonyl group, an amido group, a cyano group, anitro group, a trifluoromethyl group, a sulfoxide group, and a sulfogroup.

As the dye, well-known dyes can be used without any particularlimitation. Examples of the dye include a dye such as a pyrazole azodye, an anilino azo dye, a triarylmethane dye, an anthraquinone dye, ananthrapyridone dye, a benzylidene dye, an oxonol dye, a pyrazolotriazoleazo dye, a pyridone azo dye, a cyanine dye, a phenothiazine dye, apyrrolopyrazole azomethine dye, a xanthene dye, a phthalocyanine dye, abenzopyran dye, an indigo dye, and a pyrromethene dye. In addition, apolymer of the above-described dyes may be used. In addition, dyesdescribed in JP2015-028144A and JP2015-034966A can also be used.

Examples of the organic black colorant include a bisbenzofuranonecompound, an azomethine compound, a perylene compound, and an azocompound. Among these, a bisbenzofuranone compound or a perylenecompound is preferable. Examples of the bisbenzofuranone compoundinclude a compound described in JP2010-534726A, JP2012-515233A, andJP2012-515234A. For example, “Irgaphor Black” (manufactured by BASF SE)is available. Examples of the perylene compound include C.I. PigmentBlack 31 and 32. Examples of the azomethine compound include compoundsdescribed in JP1989-170601A (JP-H1-170601A) and JP1990-034664A(JP-H2-034664A). For example, “CHROMOFINE BLACK A1103” (manufactured byDainichiseika Color & Chemicals Mfg. Co., Ltd.) is available.

Examples of a preferable combination in the aspect (1) are as follows.

(1-1) An aspect in which the coloring material includes a red colorantand a blue colorant.

(1-2) An aspect in which the coloring material includes a red colorant,a blue colorant, and a yellow colorant.

(1-3) An aspect in which the coloring material includes a red colorant,a blue colorant, a yellow colorant, and a violet colorant.

(1-4) An aspect in which the coloring material includes a red colorant,a blue colorant, a yellow colorant, a violet colorant, and a greencolorant.

(1-5) An aspect in which the coloring material includes a red colorant,a blue colorant, a yellow colorant, and a green colorant.

(1-6) An aspect in which the coloring material includes a red colorant,a blue colorant, and a green colorant.

(1-7) An aspect in which the coloring material includes a yellowcolorant and a violet colorant.

In the aspect (2), it is preferable that the coloring material furtherincludes a chromatic colorant. By using the organic black colorant incombination with a chromatic colorant, excellent spectralcharacteristics are likely to be obtained. Examples of the chromaticcolorant which can be used in combination with the organic blackcolorant include a red colorant, a blue colorant, and a violet colorant.Among these, a red colorant or a blue colorant is preferable. Inaddition, regarding a mixing ratio between the chromatic colorant andthe organic black colorant, the amount of the chromatic colorant ispreferably 10 to 200 parts by mass and more preferably 15 to 150 partsby mass with respect to 100 parts by mass of the organic black colorant.

In a case where the photosensitive composition according to theembodiment of the present invention includes the coloring material thatblocks visible light, the content of the coloring material that blocksvisible light is preferably 3 mass % or higher, more preferably 4 mass %or higher, still more preferably 5 mass % or higher, and still morepreferably 6 mass % or higher with respect to the total solid content ofthe photosensitive composition. The upper limit is preferably 55 mass %or lower, more preferably 50 mass % or lower, and still more preferably45 mass % or lower.

In addition, the total content of the near infrared absorber and thecoloring material that blocks visible light is preferably 5 mass % orhigher, more preferably 7 mass % or higher, still more preferably 10mass % or higher, and still more preferably 12 mass % or higher withrespect to the total solid content of the photosensitive composition.The upper limit is preferably 60 mass % or lower, more preferably 55mass % or lower, and still more preferably 50 mass % or lower.

In addition, the content of the coloring material that blocks visiblelight is preferably 3 parts by mass or more, more preferably 5 parts bymass or more, still more preferably 7 parts by mass or more, and stillmore preferably 10 parts by mass or more with respect to 100 parts bymass of the near infrared absorber. The upper limit is preferably 200parts by mass or less, more preferably 190 parts by mass or less, andstill more preferably 180 parts by mass or less.

<<Photoinitiator B>>

The photosensitive composition according to the embodiment of thepresent invention includes the photoinitiator B. Examples of thephotoinitiator include a photoradical polymerization initiator and aphotocationic polymerization initiator. The photoinitiator can beselected and used depending on the kind of the compound C describedbelow. In a case where the radically polymerizable compound is used asthe compound C, it is preferable that the photoradical polymerizationinitiator is used as the photoinitiator B. In a case where thecationically polymerizable compound is used as the compound C, it ispreferable that the photocationic polymerization initiator is used asthe photoinitiator B.

It is preferable that the photoinitiator B includes at least onecompound selected from an alkylphenone compound, an acylphosphinecompound, a benzophenone compound, a thioxanthone compound, a triazinecompound, or an oxime compound, and it is more preferable that thephotoinitiator B includes an oxime compound.

Examples of the alkylphenone compound include a benzyldimethylketalcompound, an α-hydroxyalkylphenone compound, and an α-aminoalkylphenonecompound.

Examples of the benzyldimethylketal compound include2,2-dimethoxy-2-phenylacetophenone. Examples of a commercially availableproduct include IRGACURE-651 (manufactured by BASF SE).

Examples of the α-hydroxyalkylphenone compound include1-hydroxy-cyclohexyl-phenyl-ketone,2-hydroxy-2-methyl-1-phenyl-propane-1-one,1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, and2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propane-1-one.Examples of a commercially available product of theα-hydroxyalkylphenone compound include IRGACURE-184, DAROCUR-1173,IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (all of which aremanufactured by BASF SE).

Examples of the α-aminoalkylphenone compound include2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, and2-dimethylamino-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone.Examples of a commercially available product of the α-aminoalkylphenonecompound include IRGACURE-907, IRGACURE-369, and IRGACURE-379 (all ofwhich are manufactured by BASF SE).

Examples of the acylphosphine compound include2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide andbis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. Examples of acommercially available product of the acylphosphine compound includeIRGACURE-819 and IRGACURE-TPO (all of which are manufactured by BASFSE).

Examples of the benzophenone compound include benzophenone, methylo-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenylsulfide, 3,3′,4,4′-tetra(t-butyl peroxy carbonyl)benzophenone, and2,4,6′-trimethyl benzophenone.

Examples of the thioxanthone compound include 2-isopropylthioxanthone,4-isopropylthioxanthone, 2,4-diethylthioxanthone,2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

Examples of the triazine compound include2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine,2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine,2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine,2,4-bis(trichloromethyl)-6-(4-methoxyscrew)-1,3,5-triazine,2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine,2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine,2,4-bis(trichloromethyl)-6-[2-(4-di ethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, and2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxypheny)ethenyl]-1,3,5-triazine.

Examples of the oxime compound include a compound described inJP2001-233842A, a compound described in JP2000-080068A, a compounddescribed in JP2006-342166A, a compound described in J. C. S. Perkin II(1979, pp. 1653 to 1660), a compound described in J. C. S. Perkin II(1979, pp. 156 to 162), a compound described in Journal of PhotopolymerScience and Technology (1995, pp. 202 to 232), a compound described inJP2000-066385A, a compound described in JP2000-080068A, a compounddescribed in JP2004-534797A, a compound described in JP2006-342166A, acompound described in JP2017-019766A, a compound described inJP6065596B, a compound described in WO2015/152153A, and a compounddescribed in WO2017/051680A. Specific examples of the oxime compoundinclude 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one,3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one,2-acetoxyimino-1-phenylpropane-1-one,2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one, and2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. Examples of acommercially available product of the oxime compound includeIRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, or IRGACURE-OXE04 (allof which are manufactured by BASF SE), TR-PBG-304 (manufactured byChangzhou Tronly New Electronic Materials Co., Ltd.), and ADEKA OPTOMERN-1919 (manufactured by Adeka Corporation, a photopolymerizationinitiator 2 described in JP2012-014052A). As the oxime compound, acompound having no colorability or a compound having high transparencythat is not likely to discolor other components can also be preferablyused. Examples of a commercially available product of the oxime compoundinclude ADEKA ARKLS NCI-730, NCI-831, and NCI-930 (all of which aremanufactured by Adeka Corporation).

In the present invention, an oxime compound having a fluorene ring canalso be used as the photoinitiator B. Specific examples of the oximecompound having a fluorene ring include a compound described inJP2014-137466A. The content of this specification is incorporated hereinby reference.

In the present invention, an oxime compound having a fluorine atom canalso be used as the photoinitiator B. Specific examples of the oximecompound having a fluorine atom include a compound described inJP2010-262028A, Compound 24 and 36 to 40 described in JP2014-500852A,and Compound (C-3) described in JP2013-164471A. The content of thisspecification is incorporated herein by reference.

In the present invention, as the photoinitiator B, an oxime compoundhaving a nitro group can be used. It is preferable that the oximecompound having a nitro group is a dimer. Specific examples of the oximecompound having a nitro group include compounds described in paragraphs“0031” to “0047” of JP2013-114249A and paragraphs “0008” to “0012” and“0070” to “0079” of JP2014-137466A, compounds described in paragraphs“0007” to 0025” of JP4223071B, and ADEKA ARKLS NCI-831 (manufactured byAdeka Corporation).

In the present invention, as the photoinitiator B, an oxime compoundhaving a benzofuran skeleton can also be used. Specific examples includeOE-01 to OE-75 described in WO2015/036910A.

Hereinafter, specific examples of the oxime compound which arepreferably used in the present invention are shown below, but thepresent invention is not limited thereto.

In the present invention, as the photoinitiator B, a photoradicalpolymerization initiator having two functional groups or three or morefunctional groups may be used. By using this photoradical polymerizationinitiator, two or more radicals are generated from one molecule of thephotoradical polymerization initiator. Therefore, excellent sensitivitycan be obtained. In addition, in a case where a compound having anasymmetric structure is used, crystallinity deteriorates, solubility ina solvent or the like is improved, precipitation is not likely to occurover time, and temporal stability of the photosensitive composition canbe improved. Specific examples of the photoradical polymerizationinitiator having two functional groups or three or more functionalgroups include a dimer of an oxime compound described in JP2010-527339A,JP2011-524436A, WO2015/004565A, paragraphs “0412” to “0417” ofJP2016-532675A, or paragraphs “0039” to “0055” of WO2017/033680A, acompound (E) and a compound (G) described in JP2013-522445A, Cmpd 1 to 7described in WO2016/034963A, an oxime ester photoinitiator described inparagraph “0007” of JP2017-523465A, a photoinitiator described inparagraphs “0020” to “0033” of JP2017-167399A, and a photopolymerizationinitiator (A) described in paragraphs “0017” to “0026” ofJP2017-151342A.

In the present invention, a pinacol compound can also be used as thephotoinitiator B. Examples of the pinacol compound include benzopinacol,1,2-dimethoxy-1,1,2,2-tetraphenylethane,1,2-diethoxy-1,1,2,2-tetraphenylethane,1,2-diphenoxy-1,1,2,2-tetraphenylethane,1,2-dimethoxy-1,1,2,2-tetra(4-methylphenyl)ethane,1,2-diphenoxy-1,1,2,2-tetra(4-methoxyphenyl)ethane,1,2-bis(trimethylsilloxy)-1,1,2,2-tetraphenylethane,1,2-bis(triethylsilloxy)-1,1,2,2-tetraphenylethane,1,2-bis(t-butyldimethylsilloxy)-1,1,2,2-tetraphenylethane,1-hydroxy-2-trimethylsilloxy-1,1,2,2-tetraphenylethane,1-hydroxy-2-triethylsilloxy-1,1,2,2-tetraphenylethane, and1-hydroxy-2-t-butyldimethylsilloxy-1,1,2,2-tetraphenylethane. Inaddition, the details of the pinacol compound can be found inJP2014-523939A and JP2014-521772A, the contents of which areincorporated herein by reference.

In the present invention, it is preferable that the photoinitiator Bincludes the photoinitiator b1 that satisfies the following condition 1.In this aspect, a large amount of an active species such as a radical islikely to be instantaneously generated by pulse exposure, and thedesired effects of the present invention is likely to be moresignificant.

Condition 1: after a propylene glycol monomethyl ether acetate solutionincluding 0.035 mmol/L of the photoinitiator b1 is exposed to pulses oflight having a wavelength of 355 nm under conditions of a maximuminstantaneous illuminance of 375000000 W/m², pulse duration: 8nanoseconds, and frequency: 10 Hz, a quantum yield q₃₅₅ is 0.05 orhigher.

The quantum yield q₃₅₅ of the photoinitiator b1 is preferably 0.10 orhigher, more preferably 0.15 or higher, still more preferably 0.25 orhigher, still more preferably 0.35 or higher, and still more preferably0.45 or higher. In addition, the active species generated from thephotoinitiator B due to the exposure under the condition 1 is a radical.

In the this specification, the quantum yield q₃₅₅ of the photoinitiatorb1 is a value obtained by dividing the number of decomposed molecules inthe photoinitiator b1 after the pulse exposure under the condition 1 bythe number of absorbed photons in the photoinitiator b1. Regarding thenumber of absorbed photons, the number of irradiated photons is obtainedfrom the exposure time during the pulse exposure under theabove-described condition 1, an absorbance at 355 nm before and afterexposure is converted into a transmittance, and the number of irradiatedphotons is multiplied by (1-transmittance) to obtain the number ofabsorbed photons. Regarding the number of decomposed molecules, adecomposition rate of the photoinitiator b1 is obtained from theabsorbance of the photoinitiator b1 after exposure, and thedecomposition rate is multiplied by the number of molecules present inthe photoinitiator b1 to obtain the number of decomposed molecules. Inaddition, regarding the absorbance of the initiator b1, a propyleneglycol monomethyl ether acetate solution including 0.035 mmol/L of thephotoinitiator b1 is put into an optical cell of 1 cm×1 cm×4 cm, and theabsorbance of the photoinitiator b1 can be measured using aspectrophotometer. As the spectrophotometer, for example, HP8453(manufactured by Agilent Technologies Inc.) can be used. Examples of thephotoinitiator b1 that satisfies the above-described condition 1 includeIRGACURE-OXE01, OXE02, and OXE03 (all of which are manufactured by BASFSE). In addition, a compound having the following structure can bepreferably used as the photoinitiator b1 that satisfies theabove-described condition 1. In particular, from the viewpoint ofadhesiveness, IRGACURE-OXE01 and OXE02 are preferably used.

In addition, it is more preferable that the photoinitiator b1 satisfiesthe following condition 2.

Condition 2: after a film having a thickness of 1.0 μm and including 5mass % of the photoinitiator b1 and 95 mass % of a resin is exposed topulses of light having a wavelength of 265 nm under conditions of amaximum instantaneous illuminance of 375000000 W/m², pulse duration: 8nanoseconds, and frequency: 10 Hz, a quantum yield q₂₆₅ is 0.05 orhigher.

The quantum yield q₂₆₅ of the photoinitiator b1 is preferably 0.10 orhigher, more preferably 0.15 or higher, still more preferably 0.20 orhigher.

In this specification, the quantum yield q₂₆₅ of the photoinitiator b1is a value obtained by dividing the number of decomposed molecules inthe photoinitiator b1 per 1 cm² of the film after the pulse exposureunder the condition 2 by the number of absorbed photons in thephotoinitiator b1. Regarding the number of absorbed photons, the numberof irradiated photons was obtained from the exposure time during thepulse exposure under the condition 2, and the number of irradiatedphotons per 1 cm² of the film was multiplied by (1-transmittance) toobtain the number of absorbed photons. Regarding the number ofdecomposed molecules in the photoinitiator b1 per 1 cm² of the filmafter exposure, a decomposition rate of the photoinitiator b1 isobtained from a change in the absorbance of the film before and afterexposure is obtained, and the decomposition rate of the photoinitiatorb1 is multiplied by the number of molecules present in thephotoinitiator b1 per 1 cm² of the film. The weight of the film per 1cm² of the film area is obtained by setting the film density as 1.2g/cm³, and the number of molecules present in the photoinitiator b1 per1 cm² of the film is obtained as “((Weight of Film per 1 cm² of Film×5mass % (Content of PhotoInitiator b1)/Molecular Weight of PhotoInitiatorb1)×6.02×10²³ (Avogadro's Number)”.

In addition, it is preferable that the photoinitiator b1 used in thepresent invention satisfies the following condition 3.

condition 3: after a film including 5 mass % of the photoinitiator b1and a resin is exposed to one pulse of light having a wavelength in awavelength range of 248 to 365 nm under conditions of a maximuminstantaneous illuminance of 62/500,0000 W/m², pulse duration: 8nanoseconds, and frequency: 10 Hz, an active species concentration inthe film reaches 0.000000001 mmol or higher per 1 cm² of the film.

The active species concentration in the film under the condition 3 per 1cm² of the film reaches preferably 0.000000005 mmol or higher, morepreferably 0.00000001 mmol or higher, still more preferably 0.00000003mmol or higher, and still more preferably 0.0000001 mmol or higher.

In this specification, the active species concentration in theabove-described film is obtained by multiplying a quantum yield of thephotoinitiator b1 with respect to the light having a measurementwavelength by (1-transmittance of film) to calculate a decompositionrate per number of incident photons and calculating the density of thephotoinitiator b1 decomposed per 1 cm² of the film from “mol number ofphotons per one pulse”×“decomposition rate of photoinitiator b1 pernumber of incident photons”. In order to calculate the active speciesconcentration, a value calculated assuming that the entirety of thephotoinitiator b1 decomposed by light irradiation is an active species(that does not disappear during an intermediate reaction).

The resin used for the measurement under the condition 2 or 3 is notparticularly limited as long as it has compatibility to thephotoinitiator b1. For example, a resin (A) having the followingstructure is preferably used. A numerical value added to a repeatingunit represents a molar ratio, a weight-average molecular weight is40000, and a dispersity (Mn/Mw) is 5.0.

From the viewpoint of a high concentration of the active speciesgenerated, as the photoinitiator b1, an alkylphenone compound or anoxime compound is preferable, and an oxime compound is more preferable.In addition, as the photoinitiator b1, an initiator that is likely tocause two-photon absorption to occur is preferable. The two-photonabsorption refers to an excitation process of simultaneously absorbingtwo photons.

The photoinitiator B used in the present invention may consist of onlyone photoinitiator or may include two or more photoinitiators. In a casewhere the photoinitiator B includes two or more photoinitiators, each ofthe initiators may be the photoinitiator b1 that satisfies theabove-described condition 1. In addition, the photoinitiator B mayinclude one or more photoinitiators b1 that satisfy the above-describedcondition 1 and one or more photoinitiators b2 that do not satisfy theabove-described condition 1. From the viewpoint of easily generating anecessary amount of an active species, it is preferable that two or moreinitiators included in the photoinitiator B consist of only thephotoinitiator b1 that satisfies the above-described condition 1. Inaddition, from the viewpoint of easily suppressing desensitization overtime, it is preferable that two or more photoinitiators included in thephotoinitiator B includes one or more photoinitiators b1 that satisfythe above-described condition 1 and one or more photoinitiators b2 thatdo not satisfy the above-described condition 1. Examples of thephotoinitiator b2 that does not satisfy the above-described condition 1include a pinacol compound such as benzopinacol.

From the viewpoint of easily adjusting the sensitivity, it is preferablethat the photoinitiator B used in the present invention include two ormore photoinitiators.

From the viewpoint of curing properties, it is preferable that thephotoinitiator B used in the present invention satisfies the followingcondition 1a.

Condition 1a: after a propylene glycol monomethyl ether acetate solutionincluding 0.035 mmol/L of a mixture is exposed to pulses of light havinga wavelength of 355 nm under conditions of a maximum instantaneousilluminance of 375000000 W/m², pulse duration: 8 nanoseconds, andfrequency: 10 Hz, a quantum yield q₃₅₅ is preferably 0.05 or higher,more preferably 0.10 or higher, still more preferably 0.15 or higher,still more preferably 0.25 or higher, still more preferably 0.35 orhigher, and still more preferably 0.45 or higher, the mixture beingobtained by mixing two or more photoinitiators at a ratio at which thephotosensitive composition includes the two or more photoinitiators.

In addition, from the viewpoint of curing properties, it is preferablethat the photoinitiator B used in the present invention satisfies thefollowing condition 2a.

Condition 2a: after a film having a thickness of 1.0 μm and including 5mass % of a mixture and 95 mass % of a resin is exposed to pulses oflight having a wavelength of 265 nm under conditions of a maximuminstantaneous illuminance of 375000000 W/m², pulse duration: 8nanoseconds, and frequency: 10 Hz, a quantum yield q₂₆₅ is 0.05 orhigher, more preferably 0.10 or higher, still more preferably 0.15 orhigher, and still more preferably 0.20 or higher, the mixture beingobtained by mixing two or more photoinitiators at a ratio at which thephotosensitive composition includes the two or more photoinitiators.

In addition, from the viewpoint of curing properties, it is preferablethat the photoinitiator B used in the present invention satisfies thefollowing condition 3a.

Condition 3a: after a film including 5 mass % of a mixture and a resinis exposed to pulses of light having a wavelength in a wavelength rangeof 248 to 365 nm for 0.1 seconds under conditions of a maximuminstantaneous illuminance of 62/500,0000 W/m², pulse duration: 8nanoseconds, and frequency: 10 Hz, an active species concentration inthe film reaches preferably 0.000000001 mmol or higher, more preferably0.000000005 mmol or higher, still more preferably 0.00000001 mmol orhigher, still more preferably 0.00000003 mmol or higher, and mostpreferably 0.0000001 mmol or higher per 1 cm² of the film, the mixturebeing obtained by mixing two or more photoinitiators at a ratio at whichthe photosensitive composition includes the two or more photoinitiators.

From the viewpoint of sensitivity, the content of the photoinitiator Bis preferably 40 mass % or lower, more preferably 35 mass % or lower,and still more preferably 30 mass % or lower with respect to the totalsolid content of the photosensitive composition. From the viewpoint ofpattern formability, the lower limit is preferably 0.1 mass % or higher,more preferably 0.5 mass % or higher, and still more preferably 1 mass %or higher. In addition, from the viewpoint of sensitivity, the contentof the photoinitiator B is preferably 0.1 to 800 parts by mass withrespect to 100 parts by mass of the compound C described below. Theupper limit is preferably 700 parts by mass or less, more preferably 650parts by mass or less, and still more preferably 600 parts by mass orless. From the viewpoint of pattern formability, the lower limit ispreferably 0.5 parts by mass and more preferably 1 part by mass. In acase where the photosensitive composition according to the embodiment ofthe present invention includes two or more photoinitiators B, it ispreferable that the total content of the two or more photoinitiators Bis in the above-described range.

In addition, from the viewpoint of sensitivity, the content of thephotoinitiator b1 is preferably 40 mass % or lower, more preferably 35mass % or lower, and still more preferably 30 mass % or lower withrespect to the total solid content of the photosensitive composition.From the viewpoint of pattern formability, the lower limit is preferably0.1 mass % or higher, more preferably 0.5 mass % or higher, and stillmore preferably 1 mass % or higher. In addition, from the viewpoint ofsensitivity, the content of the photoinitiator b1 is preferably 0.1 to800 parts by mass with respect to 100 parts by mass of the compound Cdescribed below. The upper limit is preferably 700 parts by mass orless, more preferably 650 parts by mass or less, and still morepreferably 600 parts by mass or less. From the viewpoint of patternformability, the lower limit is preferably 0.5 parts by mass and morepreferably 1 part by mass. In a case where the photosensitivecomposition according to the embodiment of the present inventionincludes two or more photoinitiators b1, it is preferable that the totalcontent of the two or more photoinitiators b1 is in the above-describedrange.

<<Compound C>>

The photosensitive composition according to the embodiment of thepresent invention includes the compound C that is cured by reacting anactive species generated from the photoinitiator B. Examples of thecompound C include a polymerizable compound such as a radicallypolymerizable compound or a cationically polymerizable compound.Examples of the radically polymerizable compound include a compoundhaving an ethylenically unsaturated bond group such as a vinyl group, a(meth)allyl group, or a (meth)acryloyl group. Examples of thecationically polymerizable compound include a compound having a cyclicether group such as an epoxy group or an oxetanyl group.

The compound C may be a monomer (hereinafter, also referred to as“polymerizable monomer”) or a polymer (also referred to as“polymerizable polymer”. The molecular weight of the polymerizablemonomer is preferably lower than 2000, more preferably 1500 or lower,and still more preferably 1000 or lower. The lower limit is preferably100 or higher and more preferably 150 or higher. The weight-averagemolecular weight (Mw) of the polymerizable polymer is preferably 2000 to2000000. The upper limit is preferably 1000000 or lower and morepreferably 500000 or lower. The lower limit is preferably 3000 or higherand more preferably 5000 or higher. The polymerizable polymer can alsobe used as a resin described below.

In the present invention, a combination of a polymerizable monomer and apolymerizable polymer may be used as the compound C. By using acombination of a polymerizable monomer and a polymerizable polymer, afilm having a smaller thickness can be easily formed. In a case where acombination of a polymerizable monomer and a polymerizable polymer isused, the content of the polymerizable monomer is preferably 0.1 to 2000parts by mass, more preferably 0.5 to 1900 parts by mass, and still morepreferably 1 to 1800 parts by mass with respect to 100 parts by mass ofthe polymerizable polymer.

In the present invention, the compound C is preferably a radicallypolymerizable compound and more preferably a radically polymerizablemonomer. By exposing the radically polymerizable compound to pulses oflight, a radical is generated from the radically polymerizable compoundsuch that the radically polymerizable compound can be more efficientlycured, and a photosensitive composition having excellent curingproperties can be obtained. In particular, in the case of the radicallypolymerizable monomer, a radical can be more effectively generated, andthe radically polymerizable monomer can be more efficiently cured.

(Polymerizable Monomer)

The polymerizable monomer is preferably a polymerizable monomer havingtwo or more functional groups, more preferably a polymerizable monomerhaving 2 to 15 functional groups, still more preferably a polymerizablemonomer having 2 to 10 functional groups, and still more preferably apolymerizable monomer having 2 to 6 functional groups.

In addition, in the present invention, it is also preferable that apolymerizable monomer having a fluorene skeleton is used as thepolymerizable monomer. It is presumed that, even in a case where a largeamount of an active species such as a radical is instantaneouslygenerated from the photoinitiator B due to pulse exposure, for example,a self-reaction in which polymerizable groups react with each other inthe same molecule is not likely to occur in the polymerizable monomerhaving a fluorene skeleton. As a result, the polymerizable monomer canbe efficiently cured by pulse exposure, and a film having a highcrosslinking density or the like can be formed.

Examples of the polymerizable monomer having a fluorene skeleton includea compound having a partial structure represented by the followingFormula (Fr).

In the formula, a wave line represents a direct bond, R^(f1) and R^(f2)each independently represent a substituent, and m and n eachindependently represent an integer of 0 to 5. In a case where mrepresents 2 or more, m R^(f1)'s may be the same as or different fromeach other, or two R^(f1)'s among m R^(f1)'s may be bonded to each otherto form a ring. In a case where n represents 2 or more, n R^(f2)'s maybe the same as or different from each other, or two R^(f2)'s among nR^(f2)'s may be bonded to each other to form a ring. Examples of thesubstituent represented by R^(f1) and R^(f2) include a halogen atom, acyano group, a nitro group, an alkyl group, an aryl group, a heteroarylgroup, —OR^(f11), —COR^(f12), —COOR^(f13), —OCOR^(f14),—NR^(f15)R^(f16), —NHCOR^(f17), —CONR^(f18)R^(f19),—NHCONR^(f20)R^(f21), —NHCOOR^(f22), —SR^(f23), —SO₂R^(f24),—SO₂OR^(f25), —NHSO₂R^(f26), and —SO₂NR^(f27)R^(f28). R^(f11) to R^(f28)each independently represents a hydrogen atom, an alkyl group, an arylgroup, or a heteroaryl group.

The polymerizable group value of the polymerizable monomer is preferably2 mmol/g or higher, more preferably 6 mmol/g or higher, and still morepreferably 10 mmol/g or higher. From the viewpoint of refining apattern, the polymerizable group value is still more preferably 10.5mmol/g or higher. The upper limit is preferably 70 mmol/g or lower. Thepolymerizable group value of the polymerizable monomer can be calculatedby dividing the number of polymerizable groups in one molecule of thepolymerizable monomer by the molecular weight of the polymerizablemonomer.

[Radically Polymerizable Monomer]

The radically polymerizable monomer is preferably a compound having twoor more ethylenically unsaturated bond groups (compound having two ormore functional groups), more preferably a compound having 2 to 15ethylenically unsaturated bond groups (compound having 2 to 15functional groups), still more preferably a compound having 2 to 10ethylenically unsaturated bond groups (compound having 2 to 10functional groups), and still more preferably a compound having 2 to 6ethylenically unsaturated bond groups (compound having 2 to 6 functionalgroups). Specifically, the radically polymerizable monomer is preferablya (meth)acrylate compound having two or more functional groups, morepreferably a (meth)acrylate compound having 2 to 15 functional groups,still more preferably a (meth)acrylate compound having 2 to 10functional groups, and still more preferably a (meth)acrylate compoundhaving 2 to 6 functional groups. Specific examples of the polymerizablemonomer include compounds described in paragraphs “0095” to “0108” ofJP2009-288705A, paragraph “0227” of JP2013-029760 and paragraphs “0254”to “0257” of JP2008-292970A, the contents of which are incorporatedherein by reference.

The ethylenically unsaturated bond group value (hereinafter, referred toas “C═C value”) of the radically polymerizable monomer is preferably 2mmol/g or higher, more preferably 6 mmol/g or higher, and still morepreferably 10 mmol/g or higher. From the viewpoint of refining apattern, the polymerizable group value is still more preferably 10.5mmol/g or higher. The upper limit is preferably 70 mmol/g or lower. TheC═C value of the radically polymerizable monomer can be calculated bydividing the number of ethylenically unsaturated bond groups in onemolecule of the polymerizable monomer by the molecular weight of theradically polymerizable monomer.

The radically polymerizable monomer is preferably a radicallypolymerizable monomer having a fluorene skeleton and more preferably aradically polymerizable monomer having a partial structure representedby Formula (Fr). In addition, the radically polymerizable monomer havinga fluorene skeleton is preferably a compound having two or moreethylenically unsaturated bond groups, more preferably a compound having2 to 15 ethylenically unsaturated bond groups, still more preferably acompound having 2 to 10 ethylenically unsaturated bond groups, and stillmore preferably a compound having 2 to 6 ethylenically unsaturated bondgroups. Specific examples of the radically polymerizable monomer havinga fluorene skeleton include a compound having the following structure.In addition, examples of a commercially available product of theradically polymerizable monomer having a fluorene skeleton include OGSOLEA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., a(meth)acrylate monomer having a fluorene skeleton).

As the radically polymerizable monomer, compounds represented by thefollowing Formulae (MO-1) to (MO-6) can also be preferably used. In acase where T in the formulae represents an oxyalkylene group, a terminalthereof on a carbon atom side is bonded to R.

In the formulae, n represents 0 to 14, and m represents 1 to 8. Aplurality of R's and a plurality of T's which are present in onemolecule may be the same as or different from each other.

At least one of a plurality of R's which are present in each of thecompounds represented by Formula (MO-1) to (MO-6) represents—OC(═O)CH═CH₂, —OC(═O)C(CH₃)═CH₂, —NHC(═O)CH═CH₂, or —NHC(═O)C(CH₃)═CH₂.

Specific examples of the polymerizable compounds represented by Formulae(MO-1) to (MO-6) include compounds described in paragraphs “0248” to“0251” of JP2007-269779A.

It is also preferable that the radically polymerizable monomer is acompound having a caprolactone structure. As the compound having acaprolactone structure, a compound represented by the following Formula(Z-1) is preferable.

In Formula (Z-1), all of six R's represent a group represented byFormula (Z-2), or one to five R's among the six R's represent a grouprepresented by Formula (Z-2) and the remaining R's represent a grouprepresented by Formula (Z-3), an acid group, or a hydroxy group.

In Formula (Z-2), R¹ represents a hydrogen atom or a methyl group, mrepresents an integer of 1 or 2, and “*” represents a direct bond.

In Formula (Z-3), R¹ represents a hydrogen atom or a methyl group, and“*” represents a direct bond.

As the radically polymerizable monomer, a compound represented byFormula (Z-4) or (Z-5) can also be used.

In Formulae (Z-4) and (Z-5), E's each independently represent—((CH₂)_(y)CH₂O)— or —((CH₂)_(y)CH(CH₃)O)—, y's each independentlyrepresent an integer of 0 to 10, and X's each independently represent a(meth)acryloyl group, a hydrogen atom, or a carboxyl group. In Formula(Z-4), the total number of (meth)acryloyl groups is 3 or 4, m's eachindependently represent an integer of 0 to 10, and the sum of m's is aninteger of 0 to 40. In Formula (Z-5), the total number of (meth)acryloylgroups is 5 or 6, n's each independently represent an integer of 0 to10, and the sum of n's is an integer of 0 to 60.

In Formula (Z-4), m represents preferably an integer of 0 to 6 and morepreferably an integer of 0 to 4. In addition, the sum of m's ispreferably an integer of 2 to 40, more preferably an integer of 2 to 16,and still more preferably an integer of 4 to 8.

In Formula (Z-5), n represents preferably an integer of 0 to 6 and morepreferably an integer of 0 to 4. In addition, the sum of n's ispreferably an integer of 3 to 60, more preferably an integer of 3 to 24,and still more preferably an integer of 6 to 12.

In addition, it is preferable that, in —((CH₂)_(y)CH₂O)— or—((CH₂)_(y)CH(CH₃)O)— of Formula (Z-4) or (Z-5), a terminal thereof onan oxygen atom side is bonded to X.

As the radically polymerizable monomer, dipentaerythritol triacrylate(KAYARAD D-330 as a commercially available product; manufactured byNippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as acommercially available product, KAYARAD D-320 manufactured by NipponKayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (KAYARAD D-310as a commercially available product; manufactured by Nippon Kayaku Co.,Ltd.), dipentaerythritol hexa(meth)acrylate (as a commercially availableproduct, KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.; NK ESTERA-DPH-12E manufactured by Shin-Nakamura Chemical Co., Ltd.), a compoundhaving a structure in which the (meth)acryloyl group is bonded throughan ethylene glycol or a propylene glycol residue (for example, SR454 andSR499 available from Sartomer), NK ESTER A-TMMT (manufactured byShin-Nakamura Chemical Co., Ltd.), or KAYARAD RP-1040 and DPCA-20(manufactured by Nippon Kayaku Co., Ltd.) is also preferably used. Inaddition, as the radically polymerizable monomer, a trifunctional(meth)acrylate compound such as trimethylolpropane tri(meth)acrylate,trimethylolpropane propyleneoxy-modified tri(meth)acrylate,trimethylolpropane ethyleneoxy-modified tri(meth)acrylate, isocyanuricacid ethyleneoxy-modified (meth)acrylate, or pentaerythritoltri(meth)acrylate is also preferably used. Examples of a commerciallyavailable product of the trifunctional (meth)acrylate compound includeARONIX M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305,M-303, M-452, and M-450 (all of which are manufactured by Toagosei Co.,Ltd.), NK ESTER A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L,A-TMM-3LM-N, A-TMPT, and TMPT (manufactured by Shin-Nakamura ChemicalCo., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, and PET-30(manufactured by Nippon Kayaku Co., Ltd.), and TMPEOTA (manufactured byDaicel-Allnex Ltd.). As the radically polymerizable monomer, a compoundhaving an acid group such as a carboxyl group, a sulfo group, or aphosphate group is also preferably used. Examples of a commerciallyavailable product of the radically polymerizable monomer having an acidgroup include ARONIX M-305, M-510, and M-520 (manufactured by ToagoseiCo., Ltd.). The acid value of the radically polymerizable monomer havingan acid group is preferably 0.1 to 40 mgKOH/g. The lower limit ispreferably 5 mgKOH/g or higher. The upper limit is preferably 30 mgKOH/gor lower.

[Cationically Polymerizable Monomer]

The cationically polymerizable monomer is preferably a compound havingtwo or more cyclic ether groups (compound having two or more functionalgroups), more preferably a compound having 2 to 15 cyclic ether groups(compound having 2 to 15 functional groups), still more preferably acompound having 2 to 10 cyclic ether groups (compound having 2 to 10functional groups), and still more preferably a compound having 2 to 6cyclic ether groups (compound having 2 to 6 functional groups). Asspecific examples, compounds described in paragraphs “0034” to “0036” ofJP2013-011869A and paragraphs “0085” to “0090” of JP2014-089408A canalso be used. The contents of this specification are incorporated hereinby reference.

Examples of the cationically polymerizable monomer include a compoundrepresented by the following Formula (EP1).

In Formula (EP1), R^(EP1) to R^(EP3) each independently represent ahydrogen atom, a halogen atom, or an alkyl group. The alkyl group mayhave a cyclic structure or may have a substituent. In addition, R^(EP1)and R^(EP2), or R^(EP2) and R^(EP3) may be bonded to each other to forma ring structure. Q^(EP) represents a single bond or an n^(EP)-valentorganic group. R^(EP1) to R^(EP3) may be bonded to Q^(EP) to form a ringstructure. n^(EP) represents an integer of 2 or more, preferably 2 to10, and more preferably 2 to 6. In a case where Q^(EP) represents asingle bond, n^(EP) represents 2. The details of R^(EP1) to R^(EP3) andQ^(EP) can be found in paragraphs “0087” and “0088” of JP2014-089408A,the content of which is incorporated herein by reference. Specificexamples of the compound represented by Formula (EP1) include a compounddescribed in paragraph “0090” of JP2014-089408A and a compound describedin paragraph “0151” of JP2010-054632A, the contents of which areincorporated herein by reference.

Examples of a commercially available product of the cationicallypolymerizable monomer include ADEKA GLYCILOL series manufactured byAdeka Corporation (for example, ADEKA GLYCILOL ED-505) and EPOLEADseries manufactured by Daicel Corporation (for example, EPOLEAD GT401).

(Polymerizable Polymer)

Examples of the polymerizable polymer include a resin that includes arepeating unit having a polymerizable group and an epoxy resin.

Examples of the repeating unit having a polymerizable group include thefollowing (A2-1) to (A2-4).

R¹ represents a hydrogen atom or an alkyl group. The number of carbonatoms in the alkyl group is preferably 1 to 5, more preferably 1 to 3,and still more preferably 1. It is preferable that R¹ represents ahydrogen atom or a methyl group.

L⁵¹ represents a single bond or a divalent linking group. Examples ofthe divalent linking group include an alkylene group, an arylene group,—O—, —S—, —CO—, —COO—, —OCO—, —SO₂—, —NR¹⁰— (R¹⁰ represents a hydrogenatom or an alkyl group and preferably a hydrogen atom), and a groupconsisting of a combination thereof. The number of carbon atoms in thealkylene group is preferably 1 to 30, more preferably 1 to 15, and stillmore preferably 1 to 10. The alkylene group may have a substituent butis preferably unsubstituted. The alkylene group may be linear, branched,or cyclic. In addition, the cyclic alkylene group may be monocyclic orpolycyclic. The number of carbon atoms in the arylene group ispreferably 6 to 18, more preferably 6 to 14, and still more preferably 6to 10.

P¹ represents a polymerizable group. Examples of the polymerizable groupinclude: an ethylenically unsaturated bond group such as a vinyl group,a (meth)allyl group, or a (meth)acryloyl group; and a cyclic ether groupsuch as an epoxy group or an oxetanyl group.

Examples of the epoxy resin include an epoxy resin which is aglycidyl-etherified product of a phenol compound, an epoxy resin whichis a glycidyl-etherified product of various novolac resins, an alicyclicepoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, aglycidyl ester epoxy resin, a glycidyl amine epoxy resin, an epoxy resinwhich is a glycidylated product of a halogenated phenol, a condensate ofa silicon compound having an epoxy group and another silicon compound,and a copolymer of a polymerizable unsaturated compound having an epoxygroup and another polymerizable unsaturated compound. The epoxyequivalent of the epoxy resin is preferably 310 to 3300 g/eq, morepreferably 310 to 1700 g/eq, and still more preferably 310 to 1000 g/eq.Examples of a commercially available product of the epoxy resin includeEHPE 3150 (manufactured by Daicel Corporation), EPICLON N-695(manufactured by DIC Corporation), and MARPROOF G-0150M, G-0105SA,G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, orG-01758 (manufactured by NOF Corporation, an epoxy group-containingpolymer). As the epoxy resin, epoxy resins described in paragraphs“0153” to “0155” of JP2014-043556A and paragraph “0092” ofJP2014-089408A can also be used, the contents of which are incorporatedherein by reference.

As the polymerizable polymer, a resin having a fluorene skeleton canalso be preferably used. Examples of the resin having a fluoreneskeleton include a resin having the following structure. In thefollowing structural formula, A represents a residue of a carboxylicdianhydride selected from pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, ordiphenyl ether tetracarboxylic dianhydride, and M represents a phenylgroup or a benzyl group. The details of the resin having a fluoreneskeleton can be found in US2017/0102610A, the content of which isincorporated herein by reference.

The polymerizable group value of the polymerizable polymer is preferably0.5 to 3 mmol/g. The upper limit is preferably 2.5 mmol/g or lower andmore preferably 2 mmol/g or lower. The lower limit is preferably 0.9mmol/g or higher and more preferably 1.2 mmol/g or higher. Thepolymerizable group value of the polymerizable polymer refers to anumerical value representing the molar amount of the polymerizable groupvalue per 1 g of the solid content of the polymerizable polymer. Inaddition, the C═C value of the polymerizable polymer is preferably 0.6to 2.8 mmol/g. The upper limit is preferably 2.3 mmol/g or lower andmore preferably 1.8 mmol/g or lower. The lower limit is preferably 1.0mmol/g or higher and more preferably 1.3 mmol/g or higher. The C═C valueof the polymerizable polymer refers to a numerical value representingthe molar amount of the ethylenically unsaturated bond group per 1 g ofthe solid content of the polymerizable polymer.

It is also preferable that the polymerizable polymer includes arepeating unit having an acid group. The above-described polymer can beused as an alkali-soluble resin. Examples of the acid group include acarboxyl group, a phosphate group, a sulfo group, and a phenolic hydroxygroup. Among these, a carboxyl group is preferable. In a case where thepolymerizable polymer includes a repeating unit having an acid group,the acid value of the polymerizable polymer is preferably 30 to 200mgKOH/g. The lower limit is preferably 50 mgKOH/g or higher, morepreferably 70 mgKOH/g or higher, and still more preferably 100 mgKOH/gor higher. The upper limit is preferably 180 mgKOH/g or lower and morepreferably 150 mgKOH/g or lower.

Specific examples of the polymerizable polymer include a resin havingthe following structure.

The content of the compound C is preferably 0.1% to 70 mass % withrespect to the total solid content of the photosensitive composition.From the viewpoint of developability, the upper limit is preferably 60mass % or lower and more preferably 30 mass % or lower. From theviewpoint of pattern formability, the lower limit is preferably 1 mass %or higher, more preferably 2 mass % or higher, and still more preferably5 mass % or higher. The content of the compound C is more preferably 5%to 30 mass % with respect to the total solid content of thephotosensitive composition.

From the viewpoint of developability, the content of the polymerizablemonomer is preferably 70 mass % or lower, more preferably 60 mass % orlower, and still more preferably 30 mass % or lower with respect to thetotal solid content of the photosensitive composition. From theviewpoint of pattern formability, the lower limit is preferably 0.1 mass% or higher, more preferably 1 mass % or higher, still more preferably 2mass % or higher, and still more preferably 5 mass % or higher.

From the viewpoint of developability, the content of the polymerizablepolymer is preferably 70 mass % or lower, more preferably 60 mass % orlower, and still more preferably 30 mass % or lower with respect to thetotal solid content of the photosensitive composition. From theviewpoint of pattern formability, the lower limit is preferably 0.1 mass% or higher, more preferably 1 mass % or higher, still more preferably 2mass % or higher, and still more preferably 5 mass % or higher.

<<Resin>>

The photosensitive composition according to the embodiment of thepresent invention may include a resin. The resin according to theembodiment of the present invention refers to an organic compound havinga molecular weight of 2000 or higher other than the near infraredabsorber and the chromatic colorant. The resin is added, for example, inorder to disperse particles of the pigments and the like in thecomposition or to be added as a binder. The resin which is mainly usedto disperse particles of the pigments and the like will also be called adispersant. However, the above-described uses of the resin are merelyexemplary, and the resin can be used for purposes other than the uses.The resin having a polymerizable group is a component that alsocorresponds to the compound C.

The weight-average molecular weight (Mw) of the resin is preferably 2000to 2000000. The upper limit is preferably 1000000 or lower and morepreferably 500000 or lower. The lower limit is preferably 3000 or higherand more preferably 5000 or higher.

Examples of the resin include a (meth)acrylic resin, an enethiol resin,a polycarbonate resin, a polyether resin, a polyarylate resin, apolysulfone resin, a polyethersulfone resin, a polyphenylene resin, apolyarylene ether phosphine oxide resin, a polyimide resin, a polyamideimide resin, a polyolefin resin, a cyclic olefin resin, a polyesterresin, and a styrene resin. Among these resins, one kind may be usedalone, or a mixture of two or more kinds may be used. As the cyclicolefin resin, a norbornene resin can be preferably used from theviewpoint of improving heat resistance. Examples of a commerciallyavailable product of the norbornene resin include ARTON series (forexample, ARTON F4520, manufactured by JSR Corporation). In addition, asthe resin, a resin described in Examples of WO2016/088645A, a resindescribed in JP2017-057265A, a resin described in JP2017-032685A, aresin described in JP2017-075248A, or a resin described inJP2017-066240A can also be used, the contents of which are incorporatedherein by reference.

In the present invention, it is preferable that a resin having an acidgroup is used as the resin. In this aspect, the developability of thephotosensitive composition can be improved, and a pixel having excellentrectangularity can be easily formed. Examples of the acid group includea carboxyl group, a phosphate group, a sulfo group, and a phenolichydroxy group. Among these, a carboxyl group is preferable. The resinhaving an acid group can be used as, for example, an alkali-solubleresin.

It is preferable that the resin having an acid group further includes arepeating unit having an acid group at a side chain, and it is morepreferable that the content of the repeating unit having an acid groupat a side chain is preferably 5 to 70 mol % with respect to all therepeating units of the resin. The upper limit of the content of therepeating unit having an acid group at a side chain is preferably 50 mol% or lower and more preferably 30 mol % or lower. The lower limit of thecontent of the repeating unit having an acid group at a side chain ispreferably 10 mol % or higher and more preferably 20 mol % or higher.

It is preferable that the resin having an acid group is a resin whichincludes a repeating unit having a carboxyl group at a side chain.Specific examples of the resin include an alkali-soluble phenol resinsuch as a methacrylic acid copolymer, an acrylic acid copolymer, anitaconic acid copolymer, a crotonic acid copolymer, a maleic acidcopolymer, a partially esterified maleic acid copolymer, or a novolacresin, an acidic cellulose derivative having a carboxyl group at a sidechain thereof, and a resin obtained by adding an acid anhydride to apolymer having a hydroxy group. In particular, a copolymer of(meth)acrylic acid and another monomer which is copolymerizable with the(meth)acrylic acid is preferable as the alkali-soluble resin. Examplesof the monomer which is copolymerizable with the (meth)acrylic acidinclude an alkyl (meth)acrylate, an aryl (meth)acrylate, and a vinylcompound. Examples of the alkyl (meth)acrylate and the aryl(meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate,propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate,pentyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate,phenyl (meth)acrylate, benzyl (meth)acrylate, tolyl (meth)acrylate,naphthyl (meth)acrylate, and cyclohexyl (meth)acrylate. Examples of thevinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidylmethacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone,tetrahydrofurfuryl methacrylate, a polystyrene macromonomer, and apolymethyl methacrylate macromonomer. Examples of other monomers includea N-position-substituted maleimide monomer described in JP1998-300922A(JP-H10-300922A) such as N-phenylmaleimide or N-cyclohexylmaleimide. Asthe other monomer which is copolymerizable with the (meth)acrylic acid,one kind may be used alone, or two or more kinds may be used incombination. The details of the resin having an acid group can be foundin paragraphs “0558” to “0571” of JP2012-208494A (corresponding toparagraphs “0685” to “0700” of US2012/0235099A) and paragraphs “0076” to“0099” of JP2012-198408A, the contents of which are incorporated hereinby reference. In addition, as the resin having an acid group, acommercially available product may also be used. Examples of thecommercially available product include ACRYBASE FF-426 (manufactured byFujikura Kasei Co., Ltd.).

The acid value of the resin having an acid group is preferably 30 to 200mgKOH/g. The lower limit is preferably 50 mgKOH/g or higher, morepreferably 70 mgKOH/g or higher, and still more preferably 100 mgKOH/gor higher. The upper limit is preferably 180 mgKOH/g or lower and morepreferably 150 mgKOH/g or lower.

It is also preferable that the resin used in the present inventionincludes a repeating unit derived from monomer components including acompound represented by the following Formula (ED1) and/or a compoundrepresented by the following Formula (ED2) (hereinafter, these compoundswill also be referred to as “ether dimer”) is also preferable.

In Formula (ED1), R¹ and R² each independently represent a hydrogen atomor a hydrocarbon group having 1 to 25 carbon atoms which may have asubstituent.

In Formula (ED2), R represents a hydrogen atom or an organic grouphaving 1 to 30 carbon atoms. The details of Formula (ED2) can be foundin JP2010-168539A, the content of which is incorporated herein byreference.

Specific examples of the ether dimer can be found in paragraph “0317” ofJP2013-029760A, the content of which is incorporated herein byreference.

It is also preferable that the resin used in the present inventionincludes a repeating unit which is derived from a compound representedby the following Formula (X).

In Formula (X), R₁ represents a hydrogen atom or a methyl group, R₂represents an alkylene group having 2 to 10 carbon atoms, and R3represents a hydrogen atom or an alkyl group having 1 to 20 carbon atomswhich may have a benzene ring. n represents an integer of 1 to 15.

Examples of the resin having an acid group include resins having thefollowing structures.

The photosensitive composition according to the embodiment of thepresent invention may include a resin as a dispersant. Examples of thedispersant include an acidic dispersant (acidic resin) and a basicdispersant (basic resin). Here, the acidic dispersant (acidic resin)refers to a resin in which the content of an acid group is more than thecontent of a basic group. In a case where the sum of the amount of anacid group and the amount of a basic group in the acidic dispersant(acidic resin) is represented by 100 mol %, the amount of the acid groupin the acidic resin is preferably 70 mol % or higher and more preferablysubstantially 100 mol %. The acid group in the acidic dispersant (acidicresin) is preferably a carboxyl group. An acid value of the acidicdispersant (acidic resin) is preferably 40 to 105 mgKOH/g, morepreferably 50 to 105 mgKOH/g, and still more preferably 60 to 105mgKOH/g. In addition, the basic dispersant (basic resin) refers to aresin in which the amount of a basic group is more than the amount of anacid group. In a case where the sum of the amount of an acid group andthe amount of a basic group in the basic dispersant (basic resin) isrepresented by 100 mol %, the amount of the basic group in the basicresin is preferably higher than 50 mol %. The basic group in the basicdispersant is preferably an amino group.

It is preferable that the resin used as the dispersant further includesa repeating unit having an acid group. In a case where the resin used asthe dispersant further includes a repeating unit having an acid group, aphotosensitive composition having excellent developability can beobtained, and the generation of development residues can be effectivelysuppressed during the formation of a pixel using a photolithographymethod.

It is preferable that the resin used as the dispersant is a graftcopolymer. Since the graft copolymer has affinity to the solvent due tothe graft chain, the pigment dispersibility and the dispersion stabilityover time are excellent. The details of the graft copolymer can be foundin the description of paragraphs “0025” to “0094” of JP2012-255128A, thecontent of which is incorporated herein by reference. In addition,specific examples of the graft copolymer include the following resins.The following resin may also be a resin having an acid group(alkali-soluble resin). In addition, other examples of the graftcopolymer include resins described in paragraphs “0072” to “0094” ofJP2012-255128A, the content of which is incorporated herein byreference.

In addition, in the present invention, as the resin (dispersant), anoligoimine dispersant having a nitrogen atom at at least either a mainchain or a side chain is also preferably used. As the oligoiminedispersant, a resin, which includes a structural unit having a partialstructure X with a functional group (pKa: 14 or lower) and a side chainincluding a side chain Y having 40 to 10000 atoms and has a basicnitrogen atom at at least either a main chain or a side chain, ispreferable. The basic nitrogen atom is not particularly limited as longas it is a nitrogen atom exhibiting basicity. The oligoimine dispersantcan be found in the description of paragraphs “0102” to “0166” ofJP2012-255128A, the content of which is incorporated herein byreference.

In addition, it is also preferable that the resin used as a dispersantis a resin that includes a repeating unit having an ethylenicallyunsaturated bond group at a side chain. The content of the repeatingunit having an ethylenically unsaturated bond group at a side chain ispreferably 10 mol % or higher, more preferably 10% to 80 mol %, andstill more preferably 20% to 70 mol % with respect to all the repeatingunits of the resin.

The dispersant is available as a commercially available product, andspecific examples thereof include Disperbyk-111 and 161 (manufactured byBYK Chemie). In addition, a pigment dispersant described in paragraphs“0041” to “0130” of JP2014-130338A can also be used, the content ofwhich is incorporated herein by reference. In addition, the resin havingan acid group or the like can also be used as a dispersant.

The content of the resin (in a case where the compound C includes apolymerizable polymer, including the content of the polymerizablepolymer) is preferably 0.1% to 80 mass % with respect to the total solidcontent of the photosensitive composition. From the viewpoint ofdevelopability, the lower limit is preferably 0.5 mass % or higher, morepreferably 1 mass % or higher, and still more preferably 5 mass % orhigher. From the viewpoint of pattern formability, the upper limit ispreferably 75 mass % or lower, more preferably 70 mass % or lower, andstill more preferably 60 mass % or lower.

In addition, the content of the resin having an acid group (in a casewhere the compound C includes a polymerizable polymer having an acidgroup, including the content of the polymerizable polymer having an acidgroup) is preferably 0.1% to 80 mass % with respect to the total solidcontent of the photosensitive composition. From the viewpoint ofdevelopability, the lower limit is preferably 0.5 mass % or higher, morepreferably 1 mass % or higher, and still more preferably 5 mass % orhigher. From the viewpoint of pattern formability, the upper limit ispreferably 70 mass % or lower and more preferably 60 mass % or lower.

In addition, from the viewpoint of developability, the content of theresin having an acid group is preferably 1 mass % or higher, morepreferably 3 mass % or higher, still more preferably 5 mass % or higher,and still more preferably 10 mass % or higher with respect to the totalcontent of the resin. The upper limit may be 100 mass % or lower, 95mass % or lower, or 90 mass % or lower.

In addition, the total content of the polymerizable monomer and theresin is preferably 10% to 90 mass % with respect to the total solidcontent of the photosensitive composition. From the viewpoint of patternformability, the lower limit is preferably 15 mass % or higher, morepreferably 20 mass % or higher, and still more preferably 25 mass % orhigher. From the viewpoint of pattern formability, the upper limit ispreferably 85 mass % or lower, more preferably 80 mass % or lower, andstill more preferably 70 mass % or lower. In addition, the content ofthe resin is preferably 0.1 to 2000 parts by mass with respect to 100parts by mass of the polymerizable monomer. From the viewpoint ofdevelopability, the lower limit is preferably 1 part by mass or more andmore preferably 3 parts by mass or more. From the viewpoint of patternformability, the upper limit is preferably 1800 parts by mass or lessand more preferably 1500 parts by mass or less.

<<Silane Coupling Agent>>

The photosensitive composition according to the embodiment of thepresent invention may include a silane coupling agent. In a case wherethe photosensitive composition according to the embodiment of thepresent invention includes a silane coupling agent, the adhesiveness ofthe obtained film with a support can be improved. In the presentinvention, the silane coupling agent refers to a silane compound havinga functional group other than a hydrolyzable group. In addition, thehydrolyzable group refers to a substituent directly linked to a siliconatom and capable of forming a siloxane bond due to at least one of ahydrolysis reaction or a condensation reaction. Examples of thehydrolyzable group include a halogen atom, an alkoxy group, and anacyloxy group. Among these, an alkoxy group is preferable. That is, itis preferable that the silane coupling agent is a compound having analkoxysilyl group. Examples of the functional group other than ahydrolyzable group include a vinyl group, a (meth)allyl group, a(meth)acryloyl group, a mercapto group, an epoxy group, an oxetanylgroup, an amino group, an ureido group, a sulfide group, an isocyanategroup, and a phenyl group. Among these, an amino group, a (meth)acryloylgroup, or an epoxy group is preferable. Specific examples of the silanecoupling agent include a compound described in paragraphs “0018” to“0036” of JP2009-288703A and a compound described in paragraphs “0056”to “0066” of JP2009-242604A, the contents of which are incorporatedherein by reference.

The content of the silane coupling agent is preferably 0.1% to 5 mass %with respect to the total solid content of the photosensitivecomposition. The upper limit is preferably 3 mass % or lower, and morepreferably 2 mass % or lower. The lower limit is preferably 0.5 mass %or higher and more preferably 1 mass % or higher. As the silane couplingagent, one kind may be used alone, or two or more kinds may be used. Ina case where two or more surfactants are used in combination, it ispreferable that the total content of the two or more surfactants is inthe above-described range.

<<Pigment Derivative>>

The photosensitive composition according to the embodiment of thepresent invention may further include a pigment derivative. Examples ofthe pigment derivative include a compound having a structure in which aportion of a pigment is substituted with an acid group, a basic group, agroup having a salt structure, or a phthalimidomethyl group. As thepigment derivative, a compound represented by Formula (B1) ispreferable.

PL-(X)_(n))_(m)  (B1)

In Formula (B1), P represents a colorant structure, L represents asingle bond or a linking group, X represents an acid group, a basicgroup, a group having a salt structure, or a phthalimidomethyl group, mrepresents an integer of 1 or more, n represents an integer of 1 ormore, in a case where m represents 2 or more, a plurality of L's and aplurality of X's may be different from each other, and in a case where nrepresents 2 or more, a plurality of X's may be different from eachother.

The colorant structure represented by P is preferably at least oneselected from a pyrrolopyrrole colorant structure, a diketopyrrolopyrrole colorant structure, a quinacridone colorant structure, ananthraquinone colorant structure, a dianthraquinone colorant structure,a benzoisoindole colorant structure, a thiazine indigo colorantstructure, an azo colorant structure, a quinophthalone colorantstructure, a phthalocyanine colorant structure, a naphthalocyaninecolorant structure, a dioxazine colorant structure, a perylene colorantstructure, a perinone colorant structure, a benzimidazolone colorantstructure, a benzothiazole colorant structure, a benzimidazole colorantstructure, and a benzoxazole colorant structure, and more preferably atleast one selected from a pyrrolopyrrole colorant structure, a diketopyrrolo pyrrolopyrrole colorant structure, a quinacridone colorantstructure, or a benzimidazolone colorant structure.

Examples of the linking group represented by L include a hydrocarbongroup, a heterocyclic group, —NR—, —SO₂—, —S—, —O—, —CO—, and a groupconsisting of a combination thereof. R represents a hydrogen atom, analkyl group, or an aryl group.

Examples of the acid group represented by X include a carboxyl group, asulfo group, a carboxylic acid amide group, a sulfonic acid amide group,and an imide acid group. As the carboxylic acid amide group, a grouprepresented by —NHCOR^(X1) is preferable. As the sulfonic acid amidegroup, a group represented by —NHSO₂R^(X2) is preferable. As the imideacid group, a group represented by —SO₂NHSO₂R^(X3), —CONHSO₂R^(X4),—CONHCOR^(X5), or —SO₂NHCOR^(X6) is preferable. R^(X1) to R^(X6) eachindependently represent a hydrocarbon group or a heterocyclic group. Thehydrocarbon group and the heterocyclic group represented by R^(X1) toR^(X6) may further have a substituent. As the substituent which may befurther included, a halogen atom is preferable, and a fluorine atom ismore preferable. Examples of the basic group represented by X include anamino group. Examples of the salt structure represented by X include asalt of the acid group or the basic group described above.

Examples of a pigment derivative include a compound described inExamples described below. In addition, for example, compounds describedin JP1981-118462A (JP-S56-118462A), JP1988-264674A (JP-S63-264674A),JP1989-217077A (JP-H1-217077A), JP1991-009961A (JP-H3-009961A),JP1991-026767A (JP-H3-026767A), JP1991-153780A (JP-H3-153780A),JP1991-045662A (JP-H3-045662A), JP1992-285669A (JP-H4-285669A),JP1994-145546A (JP-H6-145546A), JP1994-212088A (JP-H6-212088A),JP1994-240158A (JP-H6-240158A), JP1998-030063A (JP-H10-030063A),JP1998-195326A (JP-H10-195326A), paragraphs “0086” to “0098” ofWO2011/024896A, paragraphs “0063” to “0094” of WO2012/102399A, andparagraph “0082” of WO2017/038252A can be used, the content of which isincorporated herein by reference.

The content of the pigment derivative is preferably 1 to 50 parts bymass with respect to 100 parts by mass of the pigment. The lower limitvalue is preferably 3 parts by mass or more and more preferably 5 partsby mass or more. The upper limit value is preferably 40 parts by mass orless and more preferably 30 parts by mass or less. In a case where thecontent of the pigment derivative is in the above-described range, thepigment dispersibility can be improved, and aggregation of the pigmentcan be efficiently suppressed. As the pigment derivative, one kind maybe used alone, or two or more kinds may be used in combination. In acase where two or more ultraviolet absorbers are used in combination, itis preferable that the total content of the two or more ultravioletabsorbers is in the above-described range.

<<Solvent>>

The photosensitive composition according to the embodiment of thepresent invention may include a solvent. Examples of the solvent includean organic solvent. Basically, the solvent is not particularly limitedas long as it satisfies the solubility of the respective components andthe application properties of the composition. Examples of the organicsolvent include esters, ethers, ketones, and aromatic hydrocarbons. Thedetails of the organic solvent can be found in paragraph “0223” ofWO2015/166779A, the content of which is incorporated herein byreference. In addition, an ester solvent in which a cyclic alkyl groupis substituted or a ketone solvent in which a cyclic alkyl group issubstituted can also be preferably used. Specific examples of theorganic solvent include polyethylene glycol monomethyl ether,dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate,ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethylether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone,cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitolacetate, butyl carbitol acetate, propylene glycol monomethyl ether, andpropylene glycol monomethyl ether acetate. In the present invention, asthe organic solvent, one kind may be used alone, or two or more kindsmay be used in combination. In addition,3-methoxy-N,N-dimethylpropanamide or 3-butoxy-N,N-dimethylpropanamide isalso preferable from the viewpoint of improving solubility. In thiscase, it may be preferable that the content of the aromatic hydrocarbon(for example, benzene, toluene, xylene, or ethylbenzene) as the solventis low (for example, 50 mass parts per million (ppm) or lower, 10 massppm or lower, or 1 mass ppm or lower with respect to the total mass ofthe organic solvent) in consideration of environmental aspects and thelike.

In the present invention, a solvent having a low metal content ispreferably used. For example, the metal content in the solvent ispreferably 10 mass parts per billion (ppb) or lower. Optionally, asolvent having a metal content at a mass parts per trillion (ppt) levelmay be used. For example, such a high-purity solvent is available fromToyo Gosei Co., Ltd. (The Chemical Daily, Nov. 13, 2015).

Examples of a method of removing impurities such as metal from thesolvent include distillation (for example, molecular distillation orthin-film distillation) and filtering using a filter. The pore size of afilter used for the filtering is preferably 10 μm or less, morepreferably 5 μm or less, and still more preferably 3 μm or less. As amaterial of the filter, polytetrafluoroethylene, polyethylene, or nylonis preferable.

The solvent may include an isomer (a compound having the same number ofatoms and a different structure). In addition, the organic solvent mayinclude only one isomer or a plurality of isomers.

In the present invention, as the organic solvent, an organic solventcontaining 0.8 mmol/L or lower of a peroxide is preferable, and anorganic solvent containing substantially no peroxide is more preferable.

The content of the solvent in the photosensitive composition ispreferably 10% to 95 mass %, more preferably 20% to 90 mass %, and stillmore preferably 30% to 90 mass %.

In addition, it is preferable that the photosensitive compositionaccording to the embodiment of the present invention does notsubstantially include an environmentally regulated material from theviewpoint of environmental regulations. In the present invention, notsubstantially including the environmentally regulated materialrepresents that the content of the environmentally regulated material inthe photosensitive composition is 50 mass ppm or lower, preferably 30mass ppm or lower, more preferably 10 mass ppm or lower, and still morepreferably 1 mass ppm or lower. Examples of the environmentallyregulated material include: benzene; an alkylbenzene such as toluene orxylene; and a halogenated benzene such as chlorobenzene. These compoundsare registered as environmentally regulated materials based onRegistration Evaluation Authorization and Restriction of Chemicals(REACH) regulation, Pollutant Release and Transfer Register (PRTR)method, Volatile Organic Compounds (VOC) regulation, and the like, andthe amount thereof used and a handling method thereof are strictlyregulated. These compounds are used as solvents in a case where each ofthe components or the like used in the photosensitive compositionaccording to the embodiment of the present invention is manufactured,and may be incorporated into the photosensitive composition as residualsolvents. From the viewpoints of safety for humans and consideration ofthe environment, it is preferable that these materials are reduced asmuch as possible. Examples of a method of reducing the environmentallyregulated material include a method of distilling off theenvironmentally regulated material from the system by heating ordepressurizing the system such that the temperature of the system ishigher than or equal to a boiling point of the environmentally regulatedmaterial. In addition, in a case where a small amount of environmentallyregulated material is removed by distillation, a method of azeotropingthe environmentally regulated material with a solvent having the sameboiling point as that of the corresponding solvent is also useful toincrease the efficiency. In addition, in a case where a radicallypolymerizable compound is included, in order to suppress intermolecularcrosslinking caused by the progress of a radical polymerization reactionduring distillation under reduced pressure, a polymerization inhibitoror the like may be added for distillation under reduced pressure. Thisdistillation method can be performed in, for example, any of a step ofraw materials, a step of a reaction product (for example, a resinsolution or a polyfunctional monomer solution after polymerization)obtained from a reaction of the raw materials, or a step of acomposition prepared by mixing these compounds with each other.

<<Polymerization Inhibitor>>

The photosensitive composition according to the embodiment of thepresent invention may include a polymerization inhibitor. Examples ofthe polymerization inhibitor include hydroquinone, p-methoxyphenol,di-tert-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone,4,4′-thiobis(3-methyl-6-tert-butylphenol),2,2′-methylenebis(4-methyl-6-t-butylphenol), andN-nitrosophenylhydroxyamine salt (for example, an ammonium salt or acerium (III) salt). Among these, p-methoxyphenol is preferable. Thecontent of the polymerization inhibitor is preferably 0.001% to 5 mass %with respect to the total solid content of the photosensitivecomposition.

<<Surfactant>>

The photosensitive composition according to the embodiment of thepresent invention may include a surfactant. As the surfactants, varioussurfactants such as a fluorine surfactant, a nonionic surfactant, acationic surfactant, an anionic surfactant, or a silicone surfactant canbe used. The details of the surfactant can be found in paragraphs “0238”to “0245” of WO2015/166779A, the content of which is incorporated hereinby reference.

In the present invention, it is preferable that the surfactant is afluorine surfactant. By the photosensitive composition containing afluorine surfactant, liquid characteristics (in particular, fluidity)are further improved, and liquid saving properties can be furtherimproved. In addition, a film having reduced thickness unevenness can beformed.

The fluorine content in the fluorine surfactant is preferably 3 to 40mass %, more preferably 5 to 30 mass %, and still more preferably 7 to25 mass %. The fluorine surfactant in which the fluorine content is inthe above-described range is effective from the viewpoints of theuniformity in the thickness of the coating film and liquid savingproperties, and the solubility thereof in the composition is alsoexcellent.

Examples of the fluorine surfactant include a surfactant described inparagraphs “0060” to “0064” of JP2014-041318A (paragraphs “0060” to“0064” of corresponding WO2014/017669A) and a surfactant described inparagraphs “0117” to “0132” of JP2011-132503A, the contents of which areincorporated herein by reference. Examples of a commercially availableproduct of the fluorine surfactant include: MEGAFACE F171, F172, F173,F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554,F780, EXP, and MFS-330 (all of which are manufactured by DICCorporation); FLUORAD FC430, FC431, and FC171 (all of which aremanufactured by Sumitomo 3M Ltd.); SURFLON S-382, SC-101, SC-103,SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (all of whichare manufactured by Asahi Glass Co., Ltd.); and POLYFOX PF636, PF656,PF6320, PF6520, and PF7002 (all of which are manufactured by OMNOVASolutions Inc.).

In addition, as the fluorine surfactant, an acrylic compound having amolecular structure which has a functional group having a fluorine atomand in which the functional group having a fluorine atom is cut and afluorine atom is volatilized during heat application can also bepreferably used. Examples of the fluorine surfactant include MEGAFACE DSseries (manufactured by DIC Corporation, The Chemical Daily, Feb. 22,2016, Nikkei Business Daily, Feb. 23, 2016), for example, MEGAFACEDS-21.

In addition, as the fluorine surfactant, a polymer of afluorine-containing vinyl ether compound having a fluorinated alkylgroup or a fluorinated alkylene ether group and a hydrophilic vinylether compound is also preferable. The details of this fluorinesurfactant can be found in JP2016-216602A, the content of which isincorporated herein by reference.

As the fluorine surfactant, a block polymer can also be used. Examplesof the block polymer include a compound described in JP2011-089090A. Asthe fluorine surfactant, a fluorine-containing polymer compound can bepreferably used, the fluorine-containing polymer compound including: arepeating unit derived from a (meth)acrylate compound having a fluorineatom; and a repeating unit derived from a (meth)acrylate compound having2 or more (preferably 5 or more) alkyleneoxy groups (preferably anethyleneoxy group and a propyleneoxy group). For example, the followingcompound can also be used as the fluorine surfactant used in the presentinvention.

The weight-average molecular weight of the compound is preferably 3,000to 50,000 and, for example, 14,000. In the compound, “%” representingthe proportion of a repeating unit is mol %.

In addition, as the fluorine surfactant, a fluorine-containing polymerhaving an ethylenically unsaturated bond group at a side chain can alsobe used. Specific examples include a compound described in paragraphs“0050” to “0090” and paragraphs “0289” to “0295” of JP2010-164965A, forexample, MEGAFACE RS-101, RS-102, RS-718K, and RS-72-K manufactured byDIC Corporation. As the fluorine surfactant, a compound described inparagraphs “0015” to “0158” of JP2015-117327A can also be used.

Examples of the nonionic surfactant include glycerol,trimethylolpropane, trimethylolethane, an ethoxylate and a propoxylatethereof (for example, glycerol propoxylate or glycerol ethoxylate),polyoxyethylene lauryl ether, polyoxyethylene stearyl ether,polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether,polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate,polyethylene glycol distearate, sorbitan fatty acid esters, PLURONICL10, L31, L61, L62, 10R5, 17R2, and 25R2 (manufactured by BASF SE),TETRONIC 304, 701, 704, 901, 904, and 150R1 (manufactured by BASF SE)),SOLSPERSE 20000 (manufactured by Lubrication Technology Inc.), NCW-101,NCW-1001, and NCW-1002 (all of which are manufactured by Fujifilm WakoPure Chemical Corporation), PIONIN D-6112, D-6112-W, and D-6315 (all ofwhich are manufactured by Takemoto Oil&Fat Co., Ltd.), and OLFINE E1010,SURFYNOL 104, 400, and 440 (all of which are manufactured by NissinChemical Co., Ltd.).

Examples of the silicone surfactant include: TORAY SILICONE DC3PA, TORAYSILICONE SH7PA, TORAY SILICONE DC11PA, TORAY SILICONE SH21PA, TORAYSILICONE SH28PA, TORAY SILICONE SH29PA, TORAY SILICONE SH30PA, and TORAYSILICONE SH8400 (all of which are manufactured by Dow CorningCorporation); TSF-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (allof which are manufactured by Momentive Performance Materials Inc.);KP-341, KF-6001, and KF-6002 (all of which are manufactured by Shin-EtsuChemical Co., Ltd.); and BYK307, BYK323, and BYK330 (all of which aremanufactured by BYK-Chemie Japan K.K.). In addition, as the siliconesurfactant, a compound having the following structure can also be used.

The content of the surfactant is preferably 0.001 mass % to 5.0 mass %and more preferably 0.005% to 3.0 mass % with respect to the total solidcontent of the photosensitive composition. As the surfactant, one kindmay be used alone, or two or more kinds may be used. In a case where twoor more surfactants are used in combination, it is preferable that thetotal content of the two or more surfactants is in the above-describedrange.

<<Ultraviolet Absorber>>

The photosensitive composition according to the embodiment of thepresent invention may include an ultraviolet absorber. As theultraviolet absorber, a conjugated diene compound, an amino dienecompound, a salicylate compound, a benzophenone compound, abenzotriazole compound, an acrylonitrile compound, ahydroxyphenyltriazine compound an indole compound, or a triazinecompound can be used. The details of the ultraviolet absorber can befound in paragraphs “0052” to “0072” of JP2012-208374A, paragraphs“0317” to “0334” of JP2013-068814A, and paragraphs “0061” to “0080” ofJP2016-162946A, the contents of which are incorporated herein byreference. Specific examples of the ultraviolet absorber includecompounds having the following structures. Examples of a commerciallyavailable product of the ultraviolet absorber include UV-503(manufactured by Daito Chemical Co., Ltd.). In addition, examples of thebenzotriazole compound include MYUA series (manufactured by MiyoshiOil&Fat Co., Ltd.; The Chemical Daily, Feb. 1, 2016).

The content of the ultraviolet absorber is preferably 0.01% 7 mass %with respect to the total solid content of the photosensitivecomposition. From the viewpoint of pattern formability, the upper limitis preferably 6 mass % or lower, more preferably 5 mass % or lower, andstill more preferably 4 mass % or lower. From the viewpoint ofsensitivity, the lower limit is preferably 0.05 mass % or higher andmore preferably 0.1 mass % or higher.

It is also preferable that the photosensitive composition according tothe embodiment of the present invention substantially includes anultraviolet absorber from the viewpoint of sensitivity. Thephotosensitive composition according to the embodiment of the presentinvention not substantially including an ultraviolet absorber representsthat the content of the ultraviolet absorber is preferably 0.005 mass %or lower, more preferably 0.001 mass % or lower, and still morepreferably 0 mass % with respect to the total solid content of thephotosensitive composition.

<<Antioxidant>>

The photosensitive composition according to the embodiment of thepresent invention may include an antioxidant. Examples of theantioxidant include a phenol compound, a phosphite compound, and athioether compound. As the phenol compound, any phenol compound which isknown as a phenol antioxidant can be used. Preferable examples of thephenol compound include a hindered phenol compound. A compound having asubstituent at a position (ortho position) adjacent to a phenolichydroxy group is preferable. As the substituent, a substituted orunsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Inaddition, as the antioxidant, a compound having a phenol group and aphosphite group in the same molecule is also preferable. In addition, asthe antioxidant, a phosphorus antioxidant can also be preferably used.Examples of the phosphorus antioxidant includetris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine,tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine,and ethyl bis(2,4-di-tert-butyl-6-methylphenyl)phosphite. Examples ofthe commercially available product of the antioxidant include ADEKA STABAO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50, ADEKA STABAO-50F, ADEKA STAB AO-60, ADEKA STAB AO-60G, ADEKA STAB AO-80, and ADEKASTAB AO-330 (all of which are manufactured by Adeka Corporation).

The content of the antioxidant is preferably 0.1% to 5 mass % withrespect to the total solid content of the photosensitive composition.From the viewpoint of pattern formability, the upper limit is preferably6 mass % or lower, more preferably 5 mass % or lower, and still morepreferably 4 mass % or lower. From the viewpoint of resist sensitivity,the lower limit is preferably 0.2 mass % or higher, more preferably 0.3mass % or higher, and still more preferably 0.4 mass % or higher.

From the viewpoint of resist sensitivity, it is also preferable that thephotosensitive composition according to the embodiment of the presentinvention does not substantially includes an antioxidant. Thephotosensitive composition according to the embodiment of the presentinvention not substantially including an antioxidant represents that thecontent of the antioxidant is preferably 0.05 mass % or lower, morepreferably 0.01 mass % or lower, and still more preferably 0 mass % withrespect to the total solid content of the photosensitive composition.

<<Other Components>>

Optionally, the photosensitive composition according to the embodimentof the present invention may further include a sensitizer, a curingaccelerator, a filler, a thermal curing accelerator, a plasticizer, andother auxiliary agents (for example, conductive particles, anantifoaming agent, a flame retardant, a leveling agent, a peelingaccelerator, an aromatic chemical, a surface tension adjuster, or achain transfer agent). By the composition appropriately including thecomponents, properties such as film properties can be adjusted. Thedetails of the components can be found in, for example, paragraph “0183”of JP2012-003225A (corresponding to paragraph “0237” of US2013/0034812A)and paragraphs “0101” to “0104” and “0107” to “0109” of JP2008-250074A,the contents of which are incorporated herein by reference. In addition,the photosensitive composition according to the embodiment of thepresent invention may optionally include a potential antioxidant. Thepotential antioxidant is a compound in which a portion that functions asthe antioxidant is protected by a protective group and this protectivegroup is desorbed by heating the compound at 100° C. to 250° C. or byheating the compound at 80° C. to 200° C. in the presence of an acid/abase catalyst. Examples of the potential antioxidant include a compounddescribed in WO2014/021023A, WO2017/030005A, and JP2017-008219A.Examples of a commercially available product of the potentialantioxidant include ADEKA ARKLS GPA-5001 (manufactured by AdekaCorporation).

For example, in a case where a film is formed by coating, the viscosity(23° C.) of the photosensitive composition according to the embodimentof the present invention is preferably 1 to 100 mPa·s. The lower limitis more preferably 2 mPa·s or higher and still more preferably 3 mPa·sor higher. The upper limit is preferably 50 mPa·s or lower, morepreferably 30 mPa·s or lower, and still more preferably 15 mPa·s orlower.

The concentration of solid contents of the photosensitive compositionaccording to the embodiment of the present invention is preferably 0.01%to 50 mass %. From the viewpoint of film thickness, the lower limit ispreferably 0.02 mass % or higher, more preferably 0.03 mass % or higher,and still more preferably 0.05 mass % or higher. From the viewpoint ofstorage stability, the upper limit is preferably 45 mass % or lower,more preferably 40 mass % or lower, and still more preferably 35 mass %or lower.

<Storage Container>

A storage container of the photosensitive composition according to theembodiment of the present invention is not particularly limited, and awell-known storage container can be used. In addition, as the storagecontainer, in order to suppress infiltration of impurities into the rawmaterials or the composition, a multilayer bottle in which a containerinner wall having a six-layer structure is formed of six kinds of resinsor a bottle in which a container inner wall having a seven-layerstructure is formed of six kinds of resins is preferably used. Examplesof the container include a container described in JP2015-123351A.

<Method of Preparing Photosensitive Composition>

The photosensitive composition according to the embodiment of thepresent invention can be prepared by mixing the above-describedcomponents with each other. During the preparation of the photosensitivecomposition, all the components may be dissolved or dispersed in asolvent at the same time to prepare the photosensitive composition.Optionally, two or more solutions or dispersion liquids to which therespective components are appropriately added may be prepared, and thesolutions or dispersion liquids may be mixed with each other during use(during application) to prepare the photosensitive composition.

In addition, in a case where the photosensitive composition according tothe embodiment of the present invention includes particles of a pigmentor the like, it is preferable that a process of dispersing the particlesis provided. Examples of a mechanical force used for dispersing theparticles in the process of dispersing the particles includecompression, squeezing, impact, shearing, and cavitation. Specificexamples of the process include a beads mill, a sand mill, a roll mill,a ball mill, a paint shaker, a Microfluidizer, a high-speed impeller, asand grinder, a flow jet mixer, high-pressure wet atomization, andultrasonic dispersion. During the pulverization of the particles using asand mill (beads mill), it is preferable that the process is performedunder conditions for increasing the pulverization efficiency, forexample, by using beads having a small size and increasing the fillingrate of the beads. In addition, it is preferable that coarse particlesare removed by filtering, centrifugal separation, and the like afterpulverization. In addition, as the process and the disperser fordispersing the particles, a process and a disperser described in“Complete Works of Dispersion Technology, Johokiko Co., Ltd., Jul. 15,2005”, “Dispersion Technique focusing on Suspension (Solid/LiquidDispersion) and Practical Industrial Application, ComprehensiveReference List, Publishing Department of Management Development Center,Oct. 10, 1978”, and paragraph “0022” JP2015-157893A can be suitablyused. In addition, in the process of dispersing the particles, particlesmay be refined in a salt milling step. A material, a device, processconditions, and the like used in the salt milling step can be found in,for example, JP2015-194521A and JP2012-046629A.

During the preparation of the photosensitive composition according tothe embodiment of the present invention, it is preferable that thephotosensitive composition is filtered through a filter, for example, inorder to remove foreign matter or to reduce defects. As the filter, anyfilter which is used in the related art for filtering or the like can beused without any particular limitation. Examples of a material of thefilter include: a fluororesin such as polytetrafluoroethylene (PTFE); apolyamide resin such as nylon (for example, nylon-6 or nylon-6,6); and apolyolefin resin (including a polyolefin resin having a high density andan ultrahigh molecular weight) such as polyethylene or polypropylene(PP). Among these materials, polypropylene (including high-densitypolypropylene) or nylon is preferable. The pore size of the filter issuitably about 0.01 to 7.0 μm and is preferably about 0.01 to 3.0 μm andmore preferably about 0.05 to 0.5 μm. In a case where the pore size ofthe filter is in the above-described range, fine foreign matter can bereliably removed. In addition, it is preferable that a fibrous filtermaterial is used. Examples of the fibrous filter material includepolypropylene fiber, nylon fiber, and glass fiber. Specific examplesinclude a filter cartridge of SBP type series (for example, SBP008), TPRtype series (for example, TPR002 or TPR005), and SHPX type series (forexample, SHPX003) all of which are manufactured by Roki Techno Co., Ltd.In a case where a filter is used, a combination of different filters(for example, a first filter and a second filter) may be used. At thistime, the filtering using each of the filters may be performed once, ortwice or more. In addition, a combination of filters having differentpore sizes in the above-described range may be used. In addition, thefiltering using the first filter may be performed only on the dispersionliquid, and the filtering using the second filter may be performed on amixture of the dispersion liquid and other components.

<Method of Manufacturing Optical Filter>

Next, a method of manufacturing an optical filter using thephotosensitive composition according to the embodiment of the presentinvention will be described. Examples of the kind of the optical filterinclude a near infrared cut filter and a near infrared transmittingfilter.

The method of manufacturing an optical filter according to an embodimentof the present invention includes: a step (photosensitive compositionlayer forming step) of applying the above-described photosensitivecomposition according to the embodiment of the present invention to asupport to form a photosensitive composition layer; a step (exposurestep) of exposing (pulse exposure) the photosensitive composition layerto pulses of light in a pattern shape; and a step (development step) offorming a pixel by removing a non-exposed portion of the photosensitivecomposition layer by development. Hereinafter, the respective steps willbe described.

(Photosensitive Composition Layer Forming Step)

In the photosensitive composition layer forming step, theabove-described photosensitive composition according to the embodimentof the present invention is applied to a support to form aphotosensitive composition layer. Examples of the support include asubstrate formed of a material such as silicon, non-alkali glass, sodaglass, PYREX (registered trade name) glass, or quartz glass. Inaddition, for example, an InGaAs substrate is preferably used. Inaddition, a charge coupled device (CCD), a complementary metal-oxidesemiconductor (CMOS), a transparent conductive film, or the like may beformed on the support. In addition, a black matrix that separates pixelsfrom each other may be formed on the support. In addition, optionally,an undercoat layer may be provided on the support to improveadhesiveness with a layer above the support, to prevent diffusion ofmaterials, or to make a surface of the substrate flat.

As a method of applying the photosensitive composition to the support, awell-known method can be used. Examples of the well-known methodinclude: a drop casting method; a slit coating method; a spray coatingmethod; a roll coating method; a spin coating method; a cast coatingmethod; a slit and spin method; a pre-wetting method (for example, amethod described in JP2009-145395A); various printing methods includingjet printing such as an ink jet method (for example, an on-demandmethod, a piezoelectric method, or a thermal method) or a nozzle jetmethod, flexographic printing, screen printing, gravure printing,reverse offset printing, and metal mask printing; a transfer methodusing a mold or the like; and a nanoimprint lithography method. Theapplication method using an ink jet method is not particularly limited,and examples thereof include a method (in particular, pp. 115 to 133)described in “Extension of Use of Ink Jet—Infinite Possibilities inPatent—” (February, 2005, S.B. Research Co., Ltd.) and methods describedin JP2003-262716A, JP2003-185831A, JP2003-261827A, JP2012-126830A, andJP2006-169325A. In addition, as the method of applying thephotosensitive composition, methods described in WO2017/030174A andWO2017/018419A can also be used, the contents of which are incorporatedherein by reference.

The photosensitive composition may be dried (pre-baked) after beingapplied to the support. In a case where pre-baking is performed, thepre-baking temperature is preferably 150° C. or lower, more preferably120° C. or lower, and still more preferably 110° C. or lower. The lowerlimit is, for example, 50° C. or higher or 80° C. or higher. Thepre-baking time is preferably 10 to 3000 seconds, more preferably 40 to2500 seconds, and still more preferably 80 to 2200 seconds. Drying canbe performed using a hot plate, an oven, or the like.

(Exposure Step)

Next, the photosensitive composition layer formed on the support asdescribed above is exposed (pulse exposure) to pulses of light in apattern shape. By exposing the photosensitive composition layer topulses of light through a mask having a predetermined mask pattern, thephotosensitive composition layer can be exposed to pulses of light in apattern shape. As a result, the exposed portion of the photosensitivecomposition layer can be cured.

The light used for the pulse exposure may be light having a wavelengthof longer than 300 nm or light having a wavelength of 300 nm or shorter.From the viewpoint of easily obtaining higher pattern formability orcuring properties, the light used for the exposure is preferably lighthaving a wavelength of 300 nm or shorter, more preferably light having awavelength of 270 nm or shorter, and still more preferably light havinga wavelength of 250 nm or shorter. In addition, the above-describedlight is preferably light having a wavelength of 180 nm or longer.Specific examples of the light include a KrF ray (wavelength: 248 nm)and an ArF ray (wavelength: 193 nm). From the viewpoint of easilyobtaining higher pattern formability, curing properties, and the like, aKrF ray (wavelength: 248 nm) is preferable.

It is preferable that the pulse exposure condition is the followingcondition. From the viewpoint of instantaneously generating a largeamount of an active species such as a radical easily, the pulse durationis preferably 100 nanoseconds (ns) or shorter, more preferably 50nanoseconds or shorter, and still more preferably 30 nanoseconds orshorter. The lower limit of the pulse duration is not particularlylimited and may be 1 femtoseconds (fs) or longer or 10 femtoseconds (fs)or longer. From the viewpoint of easily thermally polymerizing thecompound C due to exposure heat, the frequency is preferably 1 kHz orhigher, more preferably 2 kHz or higher, and still more preferably 4 kHzor higher. From the viewpoint of easily suppressing deformation of asubstrate or the like caused by exposure heat, the upper limit of thefrequency is preferably 50 kHz or lower, more preferably 20 kHz orlower, and still more preferably 10 kHz or lower. From the viewpoint ofcuring properties, the maximum instantaneous illuminance is preferably50000000 W/m² or higher, more preferably 100000000 W/m² or higher, andstill more preferably 200000000 W/m² or higher. In addition, from theviewpoint of high illuminance reciprocity failure, the upper limit ofthe maximum instantaneous illuminance is preferably 1000000000 W/m² orlower, more preferably 800000000 W/m² or lower, and still morepreferably 500000000 W/m² or lower. The exposure dose is preferably 1 to1000 mJ/cm². The upper limit is preferably 500 mJ/cm² or lower and morepreferably 200 mJ/cm² or lower. The lower limit is preferably 10 mJ/cm²or higher, more preferably 20 mJ/cm² or higher, and still morepreferably 30 mJ/cm² or higher.

The oxygen concentration during exposure can be appropriately selected.The exposure may be performed not only in air but also in a low-oxygenatmosphere having an oxygen concentration of 19 vol % or lower (forexample, 15 vol %, 5 vol %, or substantially 0 vol %) or in ahigh-oxygen atmosphere having an oxygen concentration of higher than 21vol % (for example, 22 vol %, 30 vol %, or 50 vol %).

(Development Step)

Next, after the exposure step, a pixel (pattern) is formed by removing anon-exposed portion of the photosensitive composition layer bydevelopment. The non-exposed portion of the photosensitive compositionlayer can be removed by development using a developer. As a result, thenon-exposed portion of the photosensitive composition layer in theexposure step is eluted into the developer, and only the portion that isphotocured in the above-described exposure step remains on the support.For example, the temperature of the developer is preferably 20° C. to30° C. The development time is preferably 20 to 180 seconds. Inaddition, in order to further improve residue removing properties, astep of shaking the developer off per 60 seconds and supplying a newdeveloper may be repeated multiple times.

As the developer, an alkaline aqueous solution in which the abovealkaline agent is diluted with pure water is preferable. Examples of thealkaline agent include: an organic alkaline compound such as ammonia,ethylamine, diethylamine, dimethylethanolamine, diglycolamine,diethanolamine, hydroxyamine, ethylenediamine, tetramethylammoniumhydroxide, tetraethylammonium hydroxide, tetrapropyl ammonium hydroxide,tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide,benzyltrimethylammonium hydroxide, dimethyl bis(2-hydroxyethyl)ammoniumhydroxide, choline, pyrrole, piperidine, or1,8-diazabicyclo[5.4.0]-7-undecene; and an inorganic alkaline compoundsuch as sodium hydroxide, potassium hydroxide, sodium carbonate, sodiumbicarbonate, sodium silicate, or sodium metasilicate. From theviewpoints of environment and safety, it is preferable that the alkalineagent is a compound having a high molecular weight. A concentration ofthe alkaline agent in the alkaline aqueous solution is preferably 0.001to 10 mass % and more preferably 0.01 to 1 mass %. In addition, thedeveloper may further include a surfactant. Examples of the surfactantinclude the above-described surfactants. Among these, a nonionicsurfactant is preferable. From the viewpoint of easiness of transport,storage, and the like, the developer may be obtained by temporarilypreparing a concentrated solution and diluting the concentrated solutionto a necessary concentration during use. The dilution factor is notparticularly limited and, for example, can be set to be in a range of1.5 to 100 times. In a case where the alkaline aqueous solution is usedas the developer, it is preferable that the layer is rinsed with purewater after development.

After the development and drying, an additional exposure treatment or aheating treatment (post-baking) can also be performed. The additionalexposure treatment or the post-baking is a treatment which is performedafter development to completely cure the film. In a case where theadditional exposure treatment is performed, as light used for theexposure, for example, a g-ray, a h-ray, or an i-ray is preferable, andan i-ray is more preferable. In addition, a combination of theabove-described rays may be used.

It is preferable that the thickness of the pixel (pattern) to be formedis appropriately selected depending on the kind of the pixel. Forexample, the thickness of the pixel is preferably 2.0 μm or less, morepreferably 1.0 μm or less, and still more preferably 0.3 to 1.0 pin. Theupper limit is preferably 0.8 μm or less and more preferably 0.6 μm orless. The lower limit value is preferably 0.4 μm or more.

In addition, it is preferable that the size (line width) of the pixel(pattern) to be formed is selected depending on the use or the kind ofthe pixel. For example, the size of the pixel is preferably 2.0 μm orless. The upper limit is preferably 1.0 μm or less and more preferably0.9 μm or less. The lower limit value is preferably 0.4 μm or more.

In a case where an optical filter including plural kinds of pixels ismanufactured, at least one kind of pixel may be formed through theabove-described steps, and it is preferable that a pixel to be initiallyformed (the first kind of pixel) is formed through the above-describedsteps. A pixel to be secondly or subsequently formed (the second orsubsequent kind of pixel) may be formed through the above-describedsteps or may be formed by exposure using continuous light.

EXAMPLES

Hereinafter, the present invention will be described in more detailusing examples. However, the present invention is not limited to thefollowing examples as long as it does not depart from the scope of thepresent invention. Unless specified otherwise, “part(s)” represents“part(s) by mass”. In addition, in the following structural formulae, Merepresents a methyl group, Et represents an ethyl group, and Phrepresents a phenyl group.

<Measurement of Weight-Average Molecular Weight (Mw) of Resin>

The weight-average molecular weight of the resin can be measured underthe following conditions by gel permeation chromatography (GPC).

Kind of column: a column in which TOSOH TSK gel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSK gel Super HZ2000 were linked to eachother

Developing solvent: tetrahydrofuran

Column temperature: 40° C.

Flow rate (sample injection volume): 1.0 μL (sample concentration: 0.1mass %)

Device name: HLC-8220 GPC (manufactured by Tosoh Corporation)

Detector: refractive index (RI) detector

Calibration curve base resin: a polystyrene resin

<Manufacturing of Pigment Dispersion Liquid>

Raw materials shown in the Table 1 below were mixed with each other, 230parts by mass of zirconia beads having a diameter of 0.3 mm were furtheradded to the mixture, and the solution was dispersed using a paintshaker for 5 hours. Next, the beads were separated by filtration. As aresult, a pigment dispersion liquid was manufactured. Numerical valuesin the following table are represented by “part(s) by mass”.

TABLE 1 Dispersing Auxiliary Agent Coloring Material and Near (PigmentDerivative Infrared Absorber or Resin) Dispersant Solvent Part(s)Part(s) Part(s) Part(s) Kind by Mass Kind by Mass Kind by Mass Kind byMass Pigment Dispersion PR254 12.00 C1 4.2 J1 83.80 Liquid R-1 PigmentDispersion PR254 8.3 B1 2.3 C2 4.4 J1 81.30 Liquid R-2 PY139 3.7 PigmentDispersion PY139 11.00 B1 1.59 C2 4.4 J1 83.01 Liquid Y-1 PigmentDispersion PY150 11.00 B1 1.59 C2 4.4 J1 83.01 Liquid Y-2 PigmentDispersion PV23 14.20 P1 2 C2 3.8 J1 70.00 Liquid V-1 J2 10.00 PigmentDispersion PB15:6 12.59 C2 4.4 J1 83.01 Liquid B-1 Pigment DispersionPB15:6 10.00 C2 4.4 J1 83.01 Liquid B-2 PV23 2.59 Pigment Dispersion IB12.59 C1 4.4 J1 83.01 Liquid Bk-1 Pigment Dispersion PBk32 12.59 C2 4.4J1 83.01 Liquid Bk-2 Pigment Dispersion PR254 6.92 C3 8.1 J1 73.9 LiquidBk-3 PY139 4.02 PB15:6 7.06 Pigment Dispersion K1 11.00 B1 1.59 C2 6 J181.41 Liquid IR-1 Pigment Dispersion K2 6.70 K3 0.8 C3 6.0 J1 86.50Liquid IR-2 Pigment Dispersion K2 6.70 K4 0.8 Liquid IR-3 C3 6.0 J186.50 Pigment Dispersion K2 6.70 K5 0.8 Liquid IR-4 C2 6 J1 86.50Pigment Dispersion K6 6.70 B1 0.8 Liquid IR-5 C2 6 J1 86.50 PigmentDispersion K7 6.70 B1 0.8 Liquid IR-6 Pigment Dispersion K8 6.70 B1 0.8C2 6 J1 86.50 Liquid IR-7

<Preparation of Photosensitive Composition>

Raw materials shown in the following table were mixed and stirred at aratio (part(s) by mass) shown in the following table, and the mixturewas filtered through a nylon filter (manufactured by Pall Corporation)having a pore size of 0.45 μm. As a result, compositions according toPreparation Examples 1 to 52 were prepared. Numerical values in thefollowing table are represented by “part(s) by mass”.

TABLE 2 Prepar- Prepar- Prepar- Prepar- Prepar- Prepar- Prepar- Prepar-Prepar- Prepar- ation ation ation ation ation ation ation ation ationation Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple 1ple 2 ple 3 ple 4 ple 5 ple 6 ple 7 ple 8 ple 9 ple 10 Near A1  3.5Infrared A2  3.5 Absorber A3  3.5 A4  3.5 A5  3.5 A6  3.5 A7  3.5 A8 3.5 A9  3.5 A10  3.5 A11 A12 A13 A14 A15 A16 A17 A18 A19 A20 A21 A22A23 Pigment R-1 Dispersion R-2 Liquid Y-1 Y-2 V-1 B-1 B-2 Bk-1 Bk-2 Bk-3IR-1 IR-2 IR-3 IR-4 IR-5 IR-6 IR-7 Poly- D1 merizable D2 Compound D3 D4D5  2.80  2.80  2.80  2.80  2.80  2.80  2.80  2.80  2.80  2.80 D7 D8Photo- I1  1.260  1.260  1.260  1.260  1.260  1.260  1.260  1.260  1.260 1.260 initiator I2 I3 I4 I5 I6 I7 I8 Resin P1 P2 P3 10.19 10.19 10.1910.19 10.19 10.19 10.19 10.19 10.19 10.19 P4 Silane H1 Coupling AgentUltraviolet U1 Absorber U2 Surfactant W1 W2  9.67  9.67  9.67  9.67 9.67  9.67  9.67  9.67  9.67  9.67 Antioxidant Y1 Poly- G1  0.0001 0.0001  0.0001  0.0001  0.0001  0.0001  0.0001  0.0001  0.0001  0.0001merization Inhibitor Solvent J1 J2 72.58 72.58 72.58 72.58 72.58 72.5872.58 72.58 72.58 72.58 J3

TABLE 3 Prepar- Prepar- Prepar- Prepar- Prepar- Prepar- Prepar- Prepar-Prepar- Prepar- ation ation ation ation ation ation ation ation ationation Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple 11ple 12 ple 13 ple 14 ple 15 ple 16 ple 17 ple 18 ple 19 ple 20 Near A1Infrared A2 Absorber A3 A4 A5 A6 A7 A8 A9 A10 A11  3.5 A12  3.5 A13  3.5A14  3.5 A15  3.5 A16  3.5 A17  3.5 A18  3.5 A19  3.5 A20  3.5 A21 A22A23 Pigment R-1 Dispersion R-2 Liquid Y-1 Y-2 V-1 B-1 B-2 Bk-1 Bk-2 Bk-3IR-1 IR-2 IR-3 IR-4 IR-5 IR-6 IR-7 Poly- D1 merizable D2 Compound D3 D4D5  2.80  2.80  2.80  2.80  2.80  2.80  2.80  2.80  2.80  2.80 D7 D8Photo- I1  1.260  1.260  1.260  1.260  1.260  1.260  1.260  1.260  1.260 1.260 initiator I2 I3 I4 I5 I6 I7 I8 Resin P1 P2 P3 10.19 10.19 10.1910.19 10.19 10.19 10.19 10.19 10.19 10.19 P4 Silane H1 Coupling AgentUltraviolet U1 Absorber U2 Surfactant W1 W2  9.67  9.67  9.67  9.67 9.67  9.67  9.67  9.67  9.67  9.67 Antioxidant Y1 Poly- G1  0.0001 0.0001  0.0001  0.0001  0.0001  0.0001  0.0001  0.0001  0.0001  0.0001merization Inhibitor Solvent J1 J2 72.58 72.58 72.58 72.58 72.58 72.5872.58 72.58 72.58 72.58 J3

TABLE 4 Prepar- Prepar- Prepar- Prepar- Prepar- Prepar- Prepar- Prepar-Prepar- Prepar- ation ation ation ation ation ation ation ation ationation Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple 21ple 22 ple 23 ple 24 ple 25 ple 26 ple 27 ple 28 ple 29 ple 30 Near A1Infrared A2 Absorber A3 A4 A5 A6 A7 A8 A9 A10 A11 A12 A13 A14 A15 A16A17 A18 A19 A20 A21  3.5 A22  3.5 A23  3.5 Pigment R-1 Dispersion R-2Liquid Y-1 Y-2 V-1 B-1 B-2 Bk-1 Bk-2 Bk-3 IR-1 IR-2 IR-3 IR-4 77.9577.95 77.95 77.95 63.20 77.95 77.95 IR-5 IR-6 IR-7 Poly- D1 merizable D2Compound D3  1.26 D4  1.26  1.10  1.42  0.65  1.50  1.26 D5  2.80  2.80 2.80 D7  1.22  1.10  1.42  0.70  1.50  1.22  1.22 D8 Photo- I1  1.260 1.260  1.260  0.784  0.784  0.784  0.500  1.027  0.784  0.600 initiatorI2  0.184 I3 I4 I5 I6 I7 I8 Resin P1 P2 P3 10.19 10.19 10.19  1.403 1.403  1.403  0.7  1.403  1.403  1.403 P4 Silane H1 Coupling AgentUltraviolet U1        0.474  0.79  0.158    0.17  0.474  0.474 AbsorberU2                     Surfactant W1        2.5  2.5  2.5  2.5  2.5  2.5 2.5 W2  9.67  9.67  9.67               Antioxidant Y1        0.158 0.158  0.158  0.158  0.17  0.158  0.158 Poly- G1  0.0001  0.0001 0.0001  0.001  0.001  0.001  0.001  0.001  0.001  0.001 merizationInhibitor Solvent J1 14.253 14.212 14.213 16.841 28.54 14.25 14.25 J272.58 72.58 72.58 J3

TABLE 5 Prepar- Prepar- Prepar- Prepar- Prepar- Prepar- Prepar- Prepar-Prepar- Prepar- ation ation ation ation ation ation ation ation ationation Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple 31ple 32 ple 33 ple 34 ple 35 ple 36 ple 37 ple 38 ple 39 ple 40 Near A1Infrared A2 Absorber A3 A4 A5 A6 A7 A8 A9 A10 A11 A12 A13 A14 A15 A16A17 A18 A19 A20 A21 A22 A23 Pigment R-1 Dispersion R-2 17.16 Liquid Y-113.14 Y-2 V-1  6.18 B-1 18.27 B-2 Bk-1 Bk-2 Bk-3 IR-1 21.50 IR-2 IR-3IR-4 77.95 77.95 77.95 77.95 77.95 77.95 IR-5 77.95 IR-6 77.95 IR-777.95 Poly- D1  0.80 merizable D2  1.00 Compound D3  0.80 D4  1.26  1.26 1.26  1.26    2.48  1.26  1.26  1.26 D5                   D7  0.72 1.22  1.22  1.22      1.22  1.22  1.22 D8          2.48         Photo-I1  0.784      0.684  0.684  0.684  0.784  0.784  0.784 initiator I2 I3 0.540 I4  0.400 I5 I6    0.784               I7      0.784            I8        0.100  0.100  0.100       Resin P1                   P2                   2.99 P3  1.403  1.403  1.403  1.403  1.403  1.403  1.403 1.403  1.403  5.98 P4                   Silane H1  0.50                Coupling                   Agent                   Ultraviolet U1  0.474 0.474  0.474  0.474  0.474  0.474  0.474  0.474  0.474  2.99 AbsorberU2  2.99 W1  2.5  2.5  2.5  2.5  2.5  2.5  2.5  2.5  2.5 Surfactant W2 0.04 Antioxidant Y1  0.158  0.158  0.158  0.158  0.158  0.158  0.158 0.158  0.158  2.99 Poly- G1  0.001  0.001  0.001  0.001  0.001  0.001 0.001  0.001  0.001  0.0013 merization Inhibitor Solvent J1 14.25 14.2514.25 14.25 14.25 14.25 14.25 14.25 14.25  2.23 J2 J3

TABLE 6 Prepar- Prepar- Prepar- Prepar- Prepar- Prepar- Prepar- Prepar-Prepar- Prepar- ation ation ation ation ation ation ation ation ationation Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple 41ple 42 ple 43 ple 44 ple 45 ple 46 ple 47 ple 48 ple 49 ple 50 Near A1Infrared A2 Absorber A3 A4 A5 A6 A7 A8 A9 A10 A11 A12 A13  3.5  3.5 1.45 A14 A15 A16 A17 A18 A19 A20 A21 A22 A23 Pigment R-1 20.45 25.69Dispersion R-2 18.49 24.37 Liquid Y-1 14.28 16.95  7.82 13.14 14.23 9.50  9.50  4.40 Y-2 V-1  6.18 B-1 27.22 15.45  8.27 24.99 12.50 12.50B-2 38.04 20.34 15.64 Bk-1 34.77 41.66 Bk-2 32.16 45.20 43.20 Bk-3 49.01IR-1 21.50 20.00 21.50 20.00 21.50 16.10 17.75 IR-2 23.73 IR-3 26.11IR-4 IR-5 IR-6 20.10 IR-7 Poly- D1  0.92  0.54  1.89  2.60  1.13  1.04 1.89 merizable D2  0.26  0.72 Compound D3  0.20 D4  0.92  2.87  0.85 D5 1.00  1.98  0.76  1.98 D7  1.00  1.98  0.76  1.98 D8 Photo- I1  0.876 0.940  0.261  0.315 initiator I2  0.793  0.344  0.910  0.340  0.344 I3 0.655  1.065 I4  0.340  0.340 I5  0.655 I6 I7 I8 Resin P1  2.45  3.41 2.53  2.95  2.88  1.64  2.3  2.33  0.53  2.95 P2 P3 P4 Silane H1  0.53Coupling Agent Ultraviolet U1 Absorber U2 Surfactant W1 W2  0.04  0.04 0.04  0.04  0.04  0.05  0.05  0.04  0.04  0.04 Antioxidant Y1  1 Poly-G1  0.0011  0.0013  0.0009  0.001  0.0013  0.0014  0.0013  0.0009 0.0009  0.001 merization Inhibitor Solvent J1 12.93 10.19  8.82  9.4322.00 19.15  3.57  8.28  8.08 10.23 J2  2 J3  1.23

TABLE 7 Preparation Preparation Example 51 Example 52 Near A1 InfraredA2 Absorber A3 A4 A5 A6 A7 A8 A9 A10 A11 A12 A13 A14 A15 A16 A17 A18 A19A20 A21 A22 A23 Pigment R-1 Dispersion R-2 Liquid Y-1 12.50 2.85 Y-2 V-1B-1 12.50 B-2 9.25 Bk-1 21.10 Bk-2 43.20 20.10 Bk-3 IR-1 7.50 IR-2 IR-3IR-4 IR-5 IR-6 20.10 20.10 IR-7 Polymerizable D1 1.89 Compound D2 D3 D4D5 1.98 D7 1.98 D8 Photoinitiator I1 I2 0.344 I3 I4 0.340 I5 0.655 I6 I7I8 Resin P1 0.53 2.95 P2 P3 P4 Silane H1 Coupling Agent Ultraviolet U1Absorber U2 Surfactant W1 W2 0.04 0.04 Antioxidant Y1 Polymerization G10.0009 0.001 Inhibitor Solvent J1 8.58 10.23 J2 J3 1.23

The raw materials shown above in the table are as follows.

(Coloring Material)

PR254: C.I. Pigment Red 254

PY139: C.I. Pigment Yellow 139

PY150: C.I. Pigment Yellow 150

PV23: C.I. Pigment Violet 23

PB15:16: C.I. Pigment Blue 15:6

IB: IRGAPHOR BLACK (manufactured by BASF SE)

PBk 32: C.I. Pigment Black 32

(Near Infrared Absorber)

A1 to A18, A20 to A23, K1, K2, K7, K8: compounds having the followingstructures

A19: NK-5060 (manufactured by Hayashibara Co., Ltd., Cyanine Compound)

K6: lanthanum boride (LaB₆—F, manufactured by Japan New Metals Co.,Ltd.)

(Pigment Derivative)

B1, K3, K4, K5: compounds having the following structures

(Dispersant)

C1: a resin having the following structure (a numerical value added to amain chain represents a molar ratio, and a numerical value added to aside chain represents the number of repeating units; Mw=20,000)

C2: a resin having the following structure (a numerical value added to amain chain represents a molar ratio, and a numerical value added to aside chain represents the number of repeating units; Mw=24,000)

C3: a resin having the following structure (a numerical value added to amain chain represents a molar ratio, and a numerical value added to aside chain represents the number of repeating units; Mw=20,000)

(Resin)

P1: a resin having the following structure (Mw=11000; a numerical valueadded to a main chain represents a molar ratio; Me represents a methylgroup)

P2: a resin having the following structure (Mw=4400, acid value=95mgKOH/g; in the following structural formula, M represents a phenylgroup, and A represents a biphenyltetracarboxylic dianhydride residue)

P3: a resin having the following structure (Mw=41400; a numerical valueadded to a main chain represents a molar ratio)

(Polymerizable Compound)

D1: a compound having the following structure (a+b+c=3, polymerizablegroup value: 7.00 mmol/g)

D2: a compound having the following structure (a+b+c=4, polymerizablegroup value: 6.34 mmol/g)

D3: a mixture of compounds having the following structures (a compoundin which a+b+c=5 (polymerizable group value=5.81 mmol/g):a compound inwhich a+b+c=6 (polymerizable group value=5.35 mmol/g)=3:1 (molar ratio))

D4: a compound having the following structure (polymerizable groupvalue: 11.35 mmol/g)

D5: a mixture of compounds having the following structures (a mixtureincluding a left side compound (polymerizable group value=10.37 mmol/g)and a right side compound (polymerizable group value=9.53 mmol/g) at amolar ratio of 7:3)

D7: ARONIX M-510 (manufactured by Toagosei Co., Ltd.)

D8: a mixture of compounds having the following structures (the contentof triacrylate: 55% to 63 mol %, polymerizable group value=10.64 mmol/g)

(Photopolymerization Initiator)

I1 to I5: compounds (oxime compounds) having the following structures

I6: IRGACURE-184 (manufactured by BASF SE)

I7: IRGACURE-TPO (manufactured by BASF SE)

I8: benzopinacol

(Silane Coupling Agent)

H1: a compound having the following structure (in the followingstructural formulae, Et represents an ethyl group)

(Ultraviolet Absorber)

U1, U2: compounds having the following structures

(Surfactant)

W1: the following mixture (Mw=14000, in the following formula, “%”representing the proportion of a repeating unit is mol %)

W2: MEGAFACE RS-72-K (manufactured by DIC Corporation, a PGMEA solutionhaving a solid content of 30 mass %)

(Antioxidant)

Y1: ADEKA STAB AO-80 (manufactured by Adeka Corporation)

(Polymerization Inhibitor)

G1: p-methoxyphenol

(Solvent)

J1: propylene glycol monomethyl ether acetate (PGMEA)

J2: cyclohexanone

J3: 3-methoxy-N,N-dimethylpropanamide

Manufacturing Examples 1 to 50

A photosensitive composition shown in the following table was applied toa glass substrate using a spin coating method such that the thickness ofthe formed film was 1 μm. Next, the coating film was heated using a hotplate at 100° C. for 2 minutes. Next, using a KrF scanner exposuredevice (manufactured by Canon Corporation, FPA-6000ES6a), the coatingfilm was exposed to pulses of light through a mask having a Bayerpattern for forming a pixel size of 1 μm×1 μm. Next, puddle developmentwas performed at 23° C. for 60 seconds using a tetramethylammoniumhydroxide (TMAH) 0.3 mass % aqueous solution. Next, the coating film wasrinsed by spin showering and was cleaned with pure water. Next, thecoating film was heated using a hot plate at 200° C. for 5 minutes toform a pattern (pixel).

The pulse exposure condition was as follows.

Exposure light: KrF ray (wavelength: 248 nm)

Exposure dose: 25 to 2000 mJ/cm²

Maximum instantaneous illuminance: 250000000 W/m² (average illuminance:30000 W/m²)

Pulse duration: 30 nanoseconds

Frequency: 4 kHz

(Manufacturing Example R1 and R2)

A photosensitive composition shown in the following table was applied toa glass substrate using a spin coating method such that the thickness ofthe formed film was 1 μm. Next, the coating film was heated using a hotplate at 100° C. for 2 minutes. Next, using an i-ray stepper exposuredevice FPA-i5+(manufactured by Canon Corporation), the coating film wasexposed through a mask having a Bayer pattern having a pixel size of 1μm×1 μm at an exposure dose of 25 to 2000 mJ/cm². The illuminance of theexposure light was substantially uniform through an exposure treatment.Next, puddle development was performed at 23° C. for 60 seconds using atetramethylammonium hydroxide (TMAH) 0.3 mass % aqueous solution. Next,the coating film was rinsed by spin showering and was cleaned with purewater. Next, the coating film was heated using a hot plate at 200° C.for 5 minutes to form a pattern (pixel).

<Evaluation of Pattern Formability>

An optimal exposure dose (Eopt) for resolving the above-describedpattern (1.0 μm×1.0 μm Bayer pattern) was determined, and the patternformability was evaluated based on the following standards. The optimalexposure dose (Eopt) refers to a minimum exposure dose at which anexposure mask size was reached.

A: Eopt was 50 mJ/cm² or higher and lower than 300 mJ/cm²

B: Eopt was 300 mJ/cm² or higher and lower than 1000 mJ/cm²

C: Eopt was 1000 mJ/cm² or higher and 1700 mJ/cm² or lower

D: Eopt was lower than 50 mJ/cm² or higher or higher than 1700 mJ/cm²

<Evaluation of Residues>

In each of the manufacturing Examples, a portion (non-exposed portion)outside of a region where a pattern was formed by exposure at theoptimal exposure dose (Eopt) was observed with a scanning electronmicroscope (SEM) (magnification of 10000 power) to evaluate developmentresidues according to the following evaluation standards.

A: in the portion (non-exposed portion) outside the region where thepattern was formed, no residues were observed

B: in the portion (non-exposed portion) outside the region where thepattern was formed, a small amount of residues were observed, but therewas no problem in practice

C: in the portion (non-exposed portion) outside the region where thepattern was formed, a significant amount of residues were observed

TABLE 8 Manufacturing Manufacturing Manufacturing ManufacturingManufacturing Example 1 Example 2 Example 3 Example 4 Example 5Photosensitive Preparation Preparation Preparation PreparationPreparation Composition Example 1 Example 2 Example 3 Example 4 Example5 Used Pattern A A A A A Formability Residue A A A A A ManufacturingManufacturing Manufacturing Manufacturing Manufacturing Example 6Example 7 Example 8 Example 9 Example 10 Photosensitive PreparationPreparation Preparation Preparation Preparation Composition Example 6Example 7 Example 8 Example 9 Example 10 Used Pattern A A A A AFormability Residue A A A A A

TABLE 9 Manufacturing Manufacturing Manufacturing ManufacturingManufacturing Example 11 Example 12 Example 13 Example 14 Example 15Photosensitive Preparation Preparation Preparation PreparationPreparation Composition Example 11 Example 12 Example 13 Example 14Example 15 Used Pattern A A A A A Formability Residue A A A A AManufacturing Manufacturing Manufacturing Manufacturing ManufacturingExample 16 Example 17 Example 18 Example 19 Example 20 PhotosensitivePreparation Preparation Preparation Preparation Preparation CompositionExample 16 Example 17 Example 18 Example 19 Example 20 Used Pattern A AA A A Formability Residue A A A A A

TABLE 10 Manufacturing Manufacturing Manufacturing ManufacturingManufacturing Example 21 Example 22 Example 23 Example 24 Example 25Photosensitive Preparation Preparation Preparation PreparationPreparation Composition Example 21 Example 22 Example 23 Example 24Example 25 Used Pattern A A A B C Formability Residue A A A A AManufacturing Manufacturing Manufacturing Manufacturing ManufacturingExample 26 Example 27 Example 28 Example 29 Example 30 PhotosensitivePreparation Preparation Preparation Preparation Preparation CompositionExample 26 Example 27 Example 28 Example 29 Example 30 Used Pattern A AA A A Formability Residue A B A A A

TABLE 11 Manufacturing Manufacturing Manufacturing ManufacturingManufacturing Example 31 Example 32 Example 33 Example 34 Example 35Photosensitive Preparation Preparation Preparation PreparationPreparation Composition Example 31 Example 32 Example 33 Example 34Example 35 Used Pattern B B B B A Formability Residue A A A A AManufacturing Manufacturing Manufacturing Manufacturing ManufacturingExample 36 Example 37 Example 38 Example 39 Example 40 PhotosensitivePreparation Preparation Preparation Preparation Preparation CompositionExample 36 Example 37 Example 38 Example 39 Example 40 Used Pattern B AA A A Formability Residue B A A A A

TABLE 12 Manufacturing Manufacturing Manufacturing ManufacturingManufacturing Example 41 Example 42 Example 43 Example 44 Example 45Photosensitive Preparation Preparation Preparation PreparationPreparation Composition Example 41 Example 42 Example 43 Example 44Example 45 Used Pattern A A A A A Formability Residue A A A A AManufacturing Manufacturing Manufacturing Manufacturing ManufacturingExample 46 Example 47 Example 48 Example 49 Example 50 PhotosensitivePreparation Preparation Preparation Preparation Preparation CompositionExample 46 Example 47 Example 48 Example 49 Example 50 Used Pattern A AA A A Formability Residue A A A A A

TABLE 13 Manufacturing Manufacturing Example R1 Example R2Photosensitive Preparation Preparation Composition Used Example 51Example 52 Pattern D D Formability Residue A A

As shown in the above-described tables, in Manufacturing Examples 1 to50 in which the films were formed by exposing the photosensitivecompositions according to Preparation Examples 1 to 50 to pulses oflight, the results of the evaluations of pattern formability andresidues were excellent.

In the compositions according to Preparation Examples 1 to 50, the sameeffects were obtained although the antioxidant, the polymerizationinhibitor, and the silane coupling agent were changed to the compoundsdescribed in this specification.

What is claimed is:
 1. A photosensitive composition for pulse exposurecomprising: a near infrared absorber A; a photoinitiator B; and acompound C that is cured by reacting with an active species generatedfrom the photoinitiator B.
 2. The photosensitive composition accordingto claim 1, wherein an A/B that is a ratio of an absorbance A of thephotosensitive composition with respect to light having a wavelength of248 nm to an absorbance B of the photosensitive composition with respectto light having a wavelength of 365 nm is 3.4 or higher.
 3. Thephotosensitive composition according to claim 1, wherein thephotoinitiator B includes an photoinitiator b1 that satisfies thefollowing condition 1, condition 1: after a propylene glycol monomethylether acetate solution including 0.035 mmol/L of the photoinitiator b1is exposed to pulses of light having a wavelength of 355 nm underconditions of a maximum instantaneous illuminance of 375000000 W/m²,pulse duration: 8 nanoseconds, and frequency: 10 Hz, a quantum yieldq₃₅₅ is 0.05 or higher.
 4. The photosensitive composition according toclaim 3, wherein the quantum yield q₃₅₅ of the photoinitiator b1 is 0.10or higher.
 5. The photosensitive composition according to claim 3,wherein the photoinitiator b1 satisfies the following condition 2,condition 2: after a film having a thickness of 1.0 μm and including 5mass % of the photoinitiator b1 and 95 mass % of a resin is exposed topulses of light having a wavelength of 265 nm under conditions of amaximum instantaneous illuminance of 375000000 W/m², pulse duration: 8nanoseconds, and frequency: 10 Hz, a quantum yield q₂₆₅ is 0.05 orhigher.
 6. The photosensitive composition according to claim 5, whereinthe quantum yield q₂₆₅ of the photoinitiator b1 is 0.10 or higher. 7.The photosensitive composition according to claim 3, wherein thephotoinitiator b1 satisfies the following condition 3, condition 3:after a film including 5 mass % of the photoinitiator b1 and a resin isexposed to one pulse of light having a wavelength in a wavelength rangeof 248 to 365 nm under conditions of a maximum instantaneous illuminanceof 62/500,0000 W/m², pulse duration: 8 nanoseconds, and frequency: 10Hz, an active species concentration in the film reaches 0.000000001 mmolor higher per 1 cm² of the film.
 8. The photosensitive compositionaccording to claim 7, wherein the active species concentration in thefilm of the photoinitiator b1 reaches 0.0000001 mmol or higher per 1 cm²of the film under the condition
 3. 9. The photosensitive compositionaccording to claim 1, wherein a content of the near infrared absorber Ais 15 mass % or higher with respect to a total solid content of thephotosensitive composition.
 10. The photosensitive composition accordingto claim 1, wherein a content of the compound C is 5% to 30 mass % withrespect to a total solid content of the photosensitive composition. 11.The photosensitive composition according to claim 1, wherein thephotoinitiator B is a photoradical polymerization initiator, and thecompound C is a radically polymerizable compound.
 12. The photosensitivecomposition according to claim 11, wherein the radically polymerizablecompound includes a radically polymerizable monomer.
 13. Thephotosensitive composition according to claim 12, wherein apolymerizable group value of the radically polymerizable monomer is 10.5mmol/g or higher.
 14. The photosensitive composition according to claim11, wherein the photoradical polymerization initiator is at least onecompound selected from an alkylphenone compound, an acylphosphinecompound, a benzophenone compound, a thioxanthone compound, a triazinecompound, or an oxime compound.
 15. The photosensitive compositionaccording to claim 1, further comprising: an ultraviolet absorber. 16.The photosensitive composition according to claim 15, wherein a contentof the ultraviolet absorber is 0.01% to 7 mass % with respect to a totalsolid content of the photosensitive composition.
 17. The photosensitivecomposition according to claim 1, further comprising: an antioxidant.18. The photosensitive composition according to claim 17, wherein acontent of the antioxidant is 0.1% to 5 mass % with respect to a totalsolid content of the photosensitive composition.
 19. The photosensitivecomposition according to claim 1, which is a composition for a nearinfrared cut filter.
 20. The photosensitive composition according toclaim 1, which is a photosensitive composition for a near infraredtransmitting filter.